Real coach Ancelotti confirmed on Monday that he is ready to unleash forward Rodriguez and midfielder Kroos on the Europa League holders in Tuesday's UEFA Super Cup final in Cardiff.
Rodriguez and Kroos are set to feature in a star-studded Real line-up that will include Gareth Bale in his homeland - and Ancelotti is also confident that Portugal captain Cristiano Ronaldo's injury problems are behind him.
Ronaldo struggled with a knee problem at the end of last season, but Ancelotti revealed that the former Manchester United man is now fully fit.
"Toni Kroos is in good shape. I think he and James will both play tomorrow," he said.
"The problems Cristiano had last season are gone and he is in shape. This is a new season for him."
Keylor Navas has also arrived at the Santiago Bernabeu ahead of the new campaign, but Ancelotti refused to reveal who his first-choice goalkeeper.
The Italian did, though, confirm that Iker Casillas will start at the Cardiff City Stadium.
"Casillas deserves to play tomorrow because he had a good Champions League last season," he added.
When asked who his number one will be, the former Milan coach said: "I don't know… or I do know but I'm not going to say."
