Molina was placed on the bereavement list Friday after his wife's grandfather died. The team said the catcher had returned to his native Puerto Rico.
Holliday was one of the hottest hitters in the majors entering the final weekend before the break, batting .500 with four home runs, 21 RBIs and 10 doubles over the last 18 games. The outfielder was batting .318 overall with 14 homers, 56 RBIs and a .397 on-base average.
"He deserved to be there and I think that's really the end of the story for me," manager Mike Matheny said before the Cardinals hosted the Marlins. "He's an All-Star player having an All-Star-caliber year and it's nice to see he's going.
"I'm real happy for Matt, especially when he's made this strong push."
It'll be the sixth All-Star appearance and third in a row for Holliday, who had been planning a fishing trip with his family. He's the sixth All-Star from the World Series champs, including starters Carlos Beltran and Rafael Furcal and reserves Lance Lynn and David Freese.
"Obviously, I feel for Yaddy and wish he could be part of the game," Holliday said. "It means a lot to me to be part of this game. To be recognized as an All-Star never gets old."
Holliday was OK with taking a break as well.
"We had a nice little trip planned, so I hadn't been following it real close," he said. "I hadn't been scrolling through the Internet."
Matheny said he wasn't sure when Molina would be back. Molina was informed of the death Friday afternoon.
"There's a lot to take care of, and he needs to be with his family," Matheny said.
Molina has long been considered one of the game's best defensive catchers and is having his best season offensively, batting .304 with 13 homers and 45 RBIs. He started 71 of St. Louis' first 83 games.
Anderson was batting .210 with two home runs and 21 RBIs in 64 games for Memphis this season.
Information from The Associated Press was used in this report.