Raiola was born in Honolulu, Hawaii. He attended Saint Louis School in Honolulu, and played for the Saint Louis Crusaders high school football team. One of his teammates was Olin Kreutz, two years his senior. The Crusaders were undefeated in his last three years at the school; in 1996, his senior year, the team won its 11th straight Prep Bowl. That same year, St. Louis High was nationally ranked as the 15th-best team in the United States.
Raiola attended the University of Nebraska at Lincoln, where he played for the Nebraska Cornhuskers football team from 1998 to 2000. In his first year, he became the first freshman offensive lineman to start a game for the Cornhuskers since 1991. In 1999, he became the first sophomore center for the team since Dave Rimington to participate in postseason play, and set a school record for knockdowns, which he bettered in 2000. Following his junior season in 2000, he won the Rimington Trophy as the best center in college football, and was recognized as a consensus first-team All-American.
Raiola was drafted by the Detroit Lions in the 2001 NFL Draft in the second round. He was the highest selected Nebraska offensive lineman since Zach Wiegert in the 1995 NFL Draft, and the highest selected center since Dave Rimington in 1983. He was also the first center drafted by the Lions since Jeff Hartings in 1996.
Raiola started to get game time as a replacement center in the latter half of the season in a game against the San Francisco 49ers in November; it was his first game in that position. He was selected as a member of Pro Football Weekly's All-Rookie squad during that season.