The two clubs have been sworn enemies since the infamous 1970 FA Cup final replay, won by the London club, was marred by nasty tackles and ill-feeling.
That match and fractious games since have ensured plenty of spite between both sets of supporters.
Leeds, now mid-table in the Championship, are chasing their third Premier League scalp of the competition having knocked out Everton and Southampton.
This is the first time the pair have met since Chelsea's 1-0 win in the 2003-04 season and Benitez will explain to his players what the fixture means.
"We will talk with them and we will explain how important is every game, how important is the competition for us and how important the game will be for all the fans and for the club," the Spaniard said.
"We will have some research about the history, I think that it is quite interesting."
Benitez's side have just returned from the Club World Cup in Japan, where they lost in the final to South American champions Corinthians.
Given the holders are already out of the Champions League and have slipped behind in the Premier League title race, the League Cup has taken on more importance as Benitez tries to convince Chelsea he should be kept on past May.
The match also has extra spice because of animosity between Benitez and Leeds manager Neil Warnock, which stems from 2007 when the Spaniard played a weakened side for Liverpool against Fulham ahead of the Champions League final.
Fulham won, a result that contributed to Warnock's Sheffield United side being relegated.
Warnock has said he is unsure if he will shake Benitez's hand before the match, although the Chelsea boss has no such issue.
"I'm professional so I will do my job. I'm professional, I will behave," he said.
Another link between the two clubs is Ken Bates, who sold Chelsea to owner Roman Abramovich in 2003 and has recently relinquished control of Leeds but stays as club president.
Chelsea will still be without the injured John Terry and striker Daniel Sturridge is doubtful.
John Obi Mikel, Gary Cahill and Ramires are suspended.
The match will be Chelsea's eighth in 24 days, but Benitez said fatigue was something they would just have to deal with.
"That's the situation and we have to manage the situation."