The France international, 34, scored Real's second goal in their 2-0 victory against Eintracht Frankfurt in Helsinki on Wednesday evening. Benzema's strike was his 324th for the Spanish giants, meaning he's now scored one more goal than club legend Raul.
Yet Benzema still has some way to go if he's to overtake the great Cristiano Ronaldo. The Portuguese superstar, 37, found the net a 450 times for Real in just 438 appearances. In comparison, Benzema needed 606 games to reach his impressive tally.
But he won't be too concerned about catching Ronaldo after lifting his first trophy since becoming Real's captain. Benzema is expected to win the Ballon d'Or later this year after inspiring his team to the La Liga title and Champions League crown last term.
"He is an amazing centre-forward," Owen Hargreaves told BT Sport. "The great players rise to these occasions. When they have needed Benzema, he has produced. If he doesn't win the Ballon d'Or this season, he never will. I can't see how he doesn't win it.
"He is irreplaceable. He will age well because he has always been a smart player. He doesn't look like he is slowing down - there isn't another one out there like him."
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Real midfielder Casemiro also believes Benzema will win the Ballon d'Or. "We didn't pay as much attention to Karim in previous years as we had a player who scored 50 goals, but Karim isn't different in terms of how he plays and the way he reads the game," he said.
"He's the best number nine in the world and remains so now. In the last two years he's gone a step further. It's obvious Karim will win the Ballon d'Or."
Ex-Real winger Steve McManaman added: "Incredible, exalted company. Huge iconic names in the history of Real Madrid - only got Cristiano above him and that says a lot. [He's had] 610 appearances to get to where he has got and he deserves all the plaudits."
It was a comfortable evening for Real in Finland. David Alaba's first-half goal broke Frankfurt's resistance before Benzema's effort all but ended the contest. It was also a famous night for Ancelotti, who became the first manager to win four UEFA Super Cups.
Real, meanwhile, have now won five UEFA Super Cups - making them the joint-most successful club in the competition's history. Bitter rivals Barcelona and Italian giants AC Milan have also lifted the trophy five times.
"After we scored the first one we had more control and we didn't take risks, didn't play with super intensity but it was a good control," said Ancelotti at full-time. "They are used to playing together, they are comfortable, they know each other. It is simple to play together, to find the right time in the game."