The accused made no comments as they arrived at the court in the eastern city of Valencia for the start of proceedings which are expected to last until September 30.
Real Zaragoza's 2-1 win on May 21, 2011, the last match of the season, spared the club relegation from the Spanish first division.
But it triggered an investigation by Spain's anti-corruption prosecutors' office over suspect payments to playing staff and coaches.
Midfielder Gabi Fernandez, who currently plays in Qatar, scored both goals in Real's crucial victory. He is among the accused along with Herrera, who moved to Paris Saint-Germain over the summer on a free transfer from Old Trafford.
Real Zaragoza's coach at the time, Mexico's Javier Aguirre, is also on trial. Aguirre was sacked as Japan's coach in 2015 over his implication in the scandal.
Prosecutors suspect Real Zaragoza deposited 965,000 euros ($1,000,000) in the bank accounts of some of its players and coaching staff so that they, in turn, could bribe Levante players to deliberately lose the game.
An investigating judge shelved the long-running probe into the match in 2017 but the case was reopened following an appeal by state prosecutors, the Spanish League and Deportivo La Coruna, the club relegated as a result of Real Zaragoza's win.
Other match-fixing scandals have erupted in Spain over the years. As recently as In May police arrested several current and former players as part of a probe into a match-fixing gang that allegedly operated in the country's first and second divisions.