Livingston was born in New York, New York in 1757 to Susanna French (d. 1789) and William Livingston (1723–1790). He received a B.A. from the College of New Jersey, (now Princeton University), in 1774. His paternal uncles were Robert Livingston (1708–1790), Peter Van Brugh Livingston (1710–1792), Philip Livingston (1716–1778), and his paternal grandparents were Philip Livingston (1686–1749), the 2nd Lord of Livingston Manor, and Catherine Van Brugh, the only child of Albany mayor Pieter Van Brugh (1666–1740).
His sister, Sarah Van Brugh Livingston (1756–1802), married John Jay (1745–1829) who was a diplomat, one of the Founding Fathers of the United States, signatory of the Treaty of Paris, the second Governor of New York, and the first Chief Justice of the United States, in 1774. Another sister, Susannah Livingston (1748–1840), married John Cleves Symmes (1742–1814), who was a delegate to the Continental Congress from New Jersey, and later a pioneer in the Northwest Territory. His daughter, Anna Symmes, from a previous marriage, married eventual President William Henry Harrison, and was the grandmother of President Benjamin Harrison.
He inherited the Livingston estate, Liberty Hall (at modern-day Kean University), and retained it until 1798. During the American Revolutionary War he was a lieutenant colonel of the New York Line, serving on the staff of General Philip Schuyler from 1775 to 1777 and as an Aide-de-Camp to Major General Benedict Arnold at the Battle of Saratoga. He was a Private secretary to John Jay, then U.S. Minister to Spain from 1779 to 1782. Livingston was briefly imprisoned by the British in New York in 1782. After the war, Livingston read law to enter the Bar in 1783, and was in private practice in New York City from 1783 to 1802.
Livingston served as a justice on the Supreme Court of New York from 1802 to 1807, where he authored a famous dissent in the case of Pierson v. Post, 3 Cai. R. 175 (1805). Two years later, on November 10, 1806, Livingston received a recess appointment from Thomas Jefferson to a seat on the Supreme Court of the United States vacated by William Paterson. Formally nominated on December 15, 1806, Livingston was confirmed by the United States Senate on December 17, 1806, and received his commission on January 16, 1807. He served on the Supreme Court from then until his death in 1823. During his Supreme Court tenure, Livingston's votes and opinions often followed the lead of Chief Justice John Marshall. In that era, Supreme Court Justices were required to ride a circuit; in Justice Livingston's case, he presided over cases in New York State.
Livingston was elected a member of the American Antiquarian Society in 1814.
In addition to being Jefferson's second appointment to the supreme court, Livingston served as a judge for the State Supreme Court of New York, a member of the New York State Assembly, and an immensely prominent political activist. Due to family ties, Livingston's allegiance to the Democratic-Republican party soon faded. Essentially, Livingston rebelled and goaded the Federalists to an enormous extent. With members consisting of Aaron Burr, Robert R. Livingston, and Edward Livingston (both cousins of Brockholst), Livingston became one of the few emerging from a compact political faction in New York to form an alliance with Jefferson's supporters in Virginia. This became known as the Virginia-New York alliance, which proved to be vital in Jefferson's 1800–1801 election.
He married three times. He first married on December 2, 1784 to Catherine Keteltas (1761–1804), the daughter of Peter Keteltas and Elizabeth Van Zandt. They were the parents of:Eliza Livingston (1786–1860), who married Jasper Hall Livingston (1780–1835), the son of Philip Philip Livingston (1741–1787)
Susan French Livingston (1789–1864), who married Benjamin Ledyard (1779–1812).
Catherine Augusta Livingston (b. c. 1790), who married Achibald McVicker (1785–1849)
Robert C. Livingston (b. c. 1793)
After his first wife's death in 1804, he married Ann N. Ludlow (1775–1815), the daughter of Gabriel Henry Ludlow and Ann Williams. Together, they were the parents of:Carroll Livingston (1805–1867), who married Cornelia Livingston.
Anson Livingston (1807–1873), who married Anne Greenleaf Livingston (1809–1887), daughter of Henry Walter Livingston (1768–1810)
After his second wife's death in 1815, he married Catherine Seaman (1775–1859), the daughter of Edward Seaman widow of Capt. John Kortright. He was the father of: They were the parents of:Jasper Hall Livingston (1815–1900), a twin, who married Matilda Anne Cecila Morris, the youngest daughter of Sir John Morris, 2nd Baronet of Clasemont, in 1851.
Catherine Louise Livingston (b. 1815), a twin, who married Maurice Power (1811–1870), an Irish MP for County Cork who served as Lieutenant Governor for St Lucia.
Henry Brockholst Livingston (1819–1892), who married Marianna Gribaldo, and resided in Italy.
Livingston died in Washington, D.C. His remains are interred at Green-Wood Cemetery in Brooklyn, N.Y.
Through his daughter Eliza, he was the great-grandfather of Edwin Brockholst Livingston (1852–1929), a historian. Through his daughter, Susan, he was the grandfather of Henry Brockholst Ledyard (1812–1880) and great-grandfather of Lewis Cass Ledyard (1851–1932). Through his daughter, Catherine McVicker, he was the grandfather of Brockholst McVicker (1810–1883) and Archibald McVicker (1816–1904). Through his daughter, Catherine Power, he was the grandfather of Brockholst Livingston Power, John Livingston Power, and Alice Livingston Power (who married her cousin, Edwin. Through his son, Henry, he was the grandfather of Oscar Enrico Federico Livingston (1875–1945). Through his son Anson, he was the grandfather of Ludlow Livingston (1838–1873), Mary Allen Livingston Harrison (1830–1921) and Ann Ludlow Livingston (1832–1913).