Rashad, a 1971 First Team All-American who played wide receiver and running back at Oregon from 1969 - 1971, will appear for the Ducks.
Jackson, who played tailback at Auburn from 1982 - 1985 and won the 1985 Heisman Trophy, will represent the Tigers.
"The excitement building around this year's national championship game is unprecedented," said Duane Woods, board chairman of the Fiesta Bowl. "Having Bo Jackson and Ahmad Rashad adds to the fervor that will be at an all-time high just before the kickoff. We are thrilled to have two of the games all-time greatest stars participate in the festivities surrounding the game."
Jackson earned induction into the College Football Hall of Fame in 1998.
Rashad, a current host and an executive producer on NBA TV, achieved the honor in 2007.
As honorary captains, the two Hall of Famers will be introduced with the current captains of each team during the coin toss on the field at University of Phoenix Stadium before the 5:30 p.m. PST game, which will be televised on ESPN.
"Bo Jackson and Ahmad Rashad are two of the greatest to ever set foot on the college gridiron," said National Football Foundation President and CEO Steven J. Hatchell. "Their legendary careers will serve as a potent reminder of the game's rich history just moments before the current generation writes the next chapter."