The son of an English mother and a Ghanaian father, Afriyie was born in Wimbledon, London, and grew up on a council estate in Peckham, attending the local Oliver Goldsmith Primary School. He was educated at Addey and Stanhope School and has a BSc, degree in agricultural economics from Wye College.
Afriyie has seven half-siblings and one brother. He said of his upbringing: "I never knew my father until I was much older and my mother, Gwen, brought us up alone. She was my rock, the gel at the centre of my life, although her tumultuous relationships with different men made for a constant state of flux at the boundaries of our family."
Afriyie is chairman of Connect Support Services, an IT support company he set up in 1993. He owned two-thirds of DeHavilland, a political monitoring company, which was sold to publishers Emap in 2005 for £18 million. He was also a regional finalist in the 2003 Ernst and Young Entrepreneur of the year awards. He was a Governor of the Museum of London, a trustee of the Museum in Docklands and a director of Policy Exchange, a centre-right policy body.
Afriyie is a stakeholder of Axonn Media, a content marketing business which produces content for clients. The company incorporates brands such as Content Plus, NewsReach, DirectNews and ReelContent. Axonn turned over £9.4m in 2011, and made a pre tax profit of £1.3m. Afriyie is the largest shareholder of the firm, and he and his fellow directors split dividends of £2.2m in 2010 and 2011, and shared directors' pay of £3.6m over the last five years.
A member of the Conservative Party since 1990, Afriye in 1999 worked for Jeffrey Archer on his unsuccessful campaign to be the first directly elected Mayor of London.
Afriyie was selected as parliamentary candidate for the constituency of Windsor in October 2003. He was first elected at the 2005 General Election, with an increased share of the vote (49.5%) and a swing to the Conservatives of 1.2%. He is the Conservative Party's first mixed-race MP, although he said in an interview with the Evening Standard that he considers himself not as black but "post-racial". In the 2010 election, Afriyie was re-elected with an increased share of the vote (60.8%) and a swing to the Conservatives of 11.4%. He made his maiden speech on 23 May 2005.
In Parliament, he was a member of the Science and Technology select committee from 2005 until its abolition in July 2007, and has since been a member of the Children, Schools and Families select committee. Since 2010 he has been the President of the Conservative Technology Forum. He has been the chair of the Parliamentary Office of Science and Technology since 2010.
Afriyie voted against the Marriage (Same Sex Couples) Bill, stating fear for religious freedom and also that he thought that straight civil partnerships should be allowed, but the bill did not.
In November 2013, Afriyie proposed an amendment to the European Union (Referendum) Bill 2013–14, to force an early vote for an early referendum on membership of the European Union, against the express wishes of his party. Afriyie continued to advocate an early referendum after his rebel amendment was easily defeated in the House of Commons with just 6% of the vote, citing public support for such a move
In December 2014, Afriyie along with six other Conservative Party MPs voted against the Equal Pay (Transparency) Bill, which would require all companies with more than 250 employees to declare the gap in pay between the average male and average female salaries. Afriyie was mooted as a possible candidate for a challenge to David Cameron for leadership of the Conservative Party, but there was little support within the party for a leadership challenge or Afriyie as a potential candidate.
In May 2004, Adam and Romi Afriyie won a libel case against The Mail on Sunday over a published article, "What IDS's Mr Perfect didn't tell Tory bosses". The article was called a "hatchet job" by Darcus Howe in the New Statesman.
In August 2005, he married his second and current wife Tracy-Jane (née Newell), a barrister and the former wife of London deputy mayor (then deputy leader of Westminster Council) Kit Malthouse.
A self made millionaire, he is worth an estimated wealth of £13m to £100m. Afryie owns a large house in Westminster, and a former seventeenth century monastery in Old Windsor called "The Priory". As of March 2016, the Priory is on the market, with an asking price of £4.85 million.