DiBernardo was raised in Naperville, Illinois where she attended Waubonsie Valley High School and helped lead the soccer team to state championship wins in 2007, 2008, and 2010. In 2009, she was named to the ESPN Rise All-American Third Team and earned Beacon News Girls Soccer Player of the Year and Chicago Sun-Times All-Area honors. During her senior year in 2010, she was named Gatorade Illinois Player of the Year, IHSSCA Illinois Player of the Year, and was ranked fifty-first in the country for high school seniors by Top Drawer Soccer.
As a freshman in 2010, DiBernardo led the Big Ten Conference in goals and points and was named the Big Ten Freshman of the Year. During her sophomore year, she led her team with 17 goals and was named to the MAC Hermann Trophy Watch List. Despite missing a portion of her junior season due to the 2012 U-20 World Cup, DiBernardo still led the Illini in points, goals, and shots. In October 2012, she was named Player of the Week by the Big Ten Conference, Top Drawer Soccer and College Sports Madness after scoring a hat-trick and helping the team defeat the University of Michigan. Unable to play the full season again due to a knee injury which kept her out for seven games, she tallied seven goals in 15 games and had a career high seven assists. DiBernardo finished her Illini career setting the school's record for most career assists and tying the school's record for most career shots. She was named to the Hermann Trophy Watch List for a third time.
In 2008, DiBernardo played for the Chicago Red Eleven in the W-League.
DiBernardo was selected as the fourth overall pick in the 2014 NWSL College Draft by the Chicago Red Stars. She previously played for Red Stars' head coach Rory Dames with the Red Stars' WPSL team in 2011 and with the Chicago Eclipse Select in 2012–2013. Of her and Julie Johnston's signing, Coach Dames said, "In Julie and Vanessa, we picked up the best holding midfielder and the best attacking midfielder in the draft. They will form the spine of our team down the middle for years to come. With both of them having the experience of winning the U20 World Cup, they are both proven winners at the highest level."
In 2014, her first year in NWSL, DiBernardo played in 23 matches out of 24 matches played by the team, and scored 1 goal and provided 3 assists.
In 2015 NWSL season DiBernardo played in all matches and almost every minutes played by the Red Stars and scored 2 goals and provide 5 assists, and was voted by fans as the team Unsung Hero.
Once again, as in 2015, DiBernardo played in all the matches in 2016 NWSL season and almost every minutes played by the Red Stars, and provided 7 assists the team highest and joint second highest in the league.
DiBernardo joined Perth Glory of the W-League on loan for the 2015–16 season. She is playing in Australia during the NWSL off-season and will return to the Chicago Red Stars for the 2016 NWSL season.
DiBernardo has represented the United States at the under-20 and under-23 levels. During the 2012 FIFA U-20 Women's World Cup, she helped the U.S. advance to the semi-finals after scoring the game-opening goal against China. The team defeated China 2–1. The team later defeated Germany 1–0 to clinch the championship. In August 2013, DiBernardo was called up to the senior national team camp ahead of a friendly match against Mexico on September 3 while still in college though she did not end up playing in the match.
DiBernado's father Angelo DiBernardo competed at 1984 Summer Olympics and other international matches, as a member of the USA men's national soccer team; they are the only father/daughter relationship among soccer players that represented USA. Her father was born in Argentina of Italian descent, so Vanessa would be eligible to play for either country's national team.