Perriello was born in, and is a lifelong resident of, Ivy, Virginia, a small unincorporated community west of Charlottesville. He is the son of Linda (née Gillooly), a financial analyst, and Vito Anthony Perriello, Jr., a pediatrician. His paternal grandparents were Italian immigrants, and his mother is from an Evangelican Christian family from Ohio. He attended Murray Elementary School, Meriwether Lewis Elementary School, Henley Middle School and Western Albemarle High School in the county school system, and then graduated from St. Anne's-Belfield School, a private school. He attained the rank of Eagle Scout in Boy Scout Troop114 in Ivy, and was a legislative page in the Virginia House of Delegates. He earned B.A. (1996) and J.D. (2001) degrees at Yale University.
From 2002-03, Perriello was Special Advisor to the international prosecutor of the Special Court for Sierra Leone, where he worked with child soldiers, amputees, and local pro-democracy groups, and helped to prosecute warlords. He later became the Court's Spokesman and helped to indict Liberian dictator Charles Taylor, peacefully forcing him from power. He has worked as a consultant to the International Center for Transitional Justice in Kosovo (2003), Darfur (2005), and Afghanistan (2007) where he worked on justice-based security strategies. Perriello has also been a fellow at The Century Foundation and consultant to the National Council of Churches of Christ. He helped to launch FaithfulAmerica.org, Catholics in Alliance for the Common Good, and is a co-founder of DarfurGenocide.org and Avaaz.org, an international on-line community of 3.3 million members, operating in 12 languages, dedicated to building a global response to "problems without borders" such as climate change. He has also worked with the Rev. James Forbes on prophetic justice principles.
Perriello, a resident of Albemarle County, has spent much of his career working in West Africa and the Middle East to create strategies for sustainable peace, and he was involved in the peace processes that helped end the civil wars in Sierra Leone and Liberia.
In announcing his first bid for Congress in 2007, Perriello credited conviction politics for his inspiration to run. "Conviction politics will make me more effective if I win. The first question I asked myself before deciding to run for office was not "can I win?" but "can I improve people's lives if I win?"
Citing the 2006 midterm elections, Perriello pointed toward the example of fellow Democrats including Senators Jim Webb, Sherrod Brown, and Jon Tester -- all winning in difficult political environments with firm positions that cut across typical progressive or conservative ideologies.
In the 2008 election, Perriello launched a campaign based on conviction politics, achieving what was described as an upset victory over entrenched Republican incumbent Virgil Goode, a longtime figure in Virginia politics who had represented a large portion of the district in the Senate of Virginia before serving in Congress.
During his time in the House of Representatives, Perriello would often explain his support for controversial votes by his standard of conviction politics. Perriello described his vote for Cap and Trade legislation as a national security imperative, stating "There’s got to be something more important than getting reelected,” in an interview with Politico. “If I lose my seat, and that’s the worst that happens, I could live with that.”
During the 2009 legislative session, Perriello voted for the American Recovery and Reinvestment Act, the American Clean Energy and Security Act, and the Patient Protection and Affordable Care Act in March 2010.
Perriello voted against the Unemployment Compensation Extension Act of 2009, because the bill extended unemployment benefits for only some states and excluded Virginia.
Perriello is a supporter of the War on Terror. Although he cast votes for the continuation of U.S. military action in Afghanistan, he also cosponsored legislation requiring U.S. President Barack Obama to submit an exit strategy for the end of combat operations in Afghanistan. Perriello also opposed removing the United States Armed Forces from Pakistan. In 2010, Perriello voted in support of the defense bill, 2010 military appropriations and spending for combat operations.