Carlo Ancelotti's side beat Barcelona in a five-goal thriller to advance to the final, while Athletic secured their spot in Sunday's contest courtesy of a 2-1 success over Atletico Madrid.
Benzema was in impressive form against Barcelona, scoring once and providing one assist, with the Frenchman enjoying a strong 2021-22 campaign.
The centre-forward has found the back of the net on 23 occasions in 26 appearances in all competitions this season, in addition to contributing nine assists.
Here, Sports Mole looks at how Benzema has fared against the Basque side in the past, as both teams prepare for the final of the Spanish Super Cup this weekend.
Benzema has faced Athletic 26 times during his Real Madrid career and boasts an excellent record against the Basque side, winning 18 times, drawing five and losing on just three occasions.
The Frenchman has managed 17 goals and six assists against Athletic, meanwhile, including three goals in the two La Liga fixtures between the two sides during the 2021-22 campaign, netting the winner at Bernabeu on December 1 before striking twice at San Mames later in the month.
Benzema also scored against Athletic in the semi-finals of the Spanish Super Cup last year but could not prevent his side from suffering a 2-1 defeat to the eventual winners.
The forward's La Liga record against Athletic is 18 wins, five draws and two defeats from 25 matches, while he has scored 16 times and provided six assists, and his overall record of 17 goals means that he has netted more times against the Lions than any other side in his professional career.
The forward has scored braces against the Basque side on four separate occasions, including on their last meeting towards the end of December, so he should enter this match full of confidence.
Arguably, though, Benzema's finest ever display against Athletic came in Madrid back in April 2019, when he scored three times in a 3-0 home success.
The forward has not actually lost to Athletic in the league since March 2015, but the fact that the Basque side triumphed in their Spanish Super Cup meeting last year must be taken into consideration.
This competition is down the pecking order when it comes to Real Madrid's ambitions for the second half of the season, but it provides Ancelotti with the chance to win some early silverware in his second spell in charge.
Benzema has had so much success against Athletic in the past, meanwhile, and the fact that Los Blancos will have had an extra day of recovery for the final could play a huge part in how this match unfolds.