Benitez is still smarting over the 2-1 defeat by AC Milan, and this time around he will have £40million plus of new players to help him ease the pain of that defeat in Greece.
The Spaniard was able to leave Peter Crouch, Yossi Benayoun, Javier Mascherano and Harry Kewell back home on Merseyside on Saturday when Liverpool opened their Barclays Premier League campaign with a 2-1 success at Aston Villa.
It is reported that Crouch was unimpressed and had talks with Benitez, but the club today would not confirm that and predictably played down any suggestion of friction.
For the trip to Toulouse, Crouch, Mascherano and Benayoun were included, Kewell is still nursing a groin injury, while Jermaine Pennant was left at home.
The fact four seasoned internationals could not even find a seat on the coach for Saturday's opener says everything about life at Anfield now.
Benitez will shuffle his pack again in south-west France - he has two men for every position and enough riches, he claims, to go for everything this term.
However, he still cannot get Athens out of his mind, so Toulouse can expect a very demanding night in their own Municipal stadium.
The Spaniard explained: I am still not over that game in Athens. Especially because we came so close to winning.
"I think about it all the time, how we could have won. Two finals in three years was a fantastic achievement, but now I want three finals in four years."
Benitez admits to replaying the video of Athens over and over again - but Steven Gerrard feels differently.
The captain said: "I don't have to keep looking at what went wrong, I know, and that makes me and everyone else more determined to put things right."
Liverpool are expected to come through this final qualifying round into the lucrative group stages, but one result at the weekend will have concentrated a few minds at Anfield on the task in hand against the side who finished a surprise third in the French League last term.
That result was: Toulouse 1 Lyon 0. The French champions for the past six seasons beaten by the European new boys.
The winning goal came from Swedish striker Johan Elmander, who has just declined the offer of a new contract claiming: "I still have three years left of my current deal."
Toulouse, knowing Marseille, Manchester City and West Ham are believed to be interested, wanted to secure their leading scorer on a new deal.
Now they are just desperate for him to recover from a thigh injury to face Liverpool in tomorrow's first leg.
Liverpool's Daniel Agger was a team-mate of Elmander's at Bromby and will know the threat he poses.
This is Toulouse's first time in the competition, but Benitez will not be fooled by their coach Elie Baup saying: "It's more than a mountain to climb - it's the Himalayas."
Only eight years ago Toulouse were playing third division football and in recent seasons the club have been more accustomed to fighting relegation than contemplating Europe.
Now Baup says: "In some ways it is the best draw we could have hoped for. It has created a buzz around the club as Toulouse are not a big name in French football."
With Liverpool making a clear statement about where their priorities are this term in terms of trying to win the title after 17 years of failure, it would be easy to suggest that Europe may not be as high on their target list this term.
But Gerrard will have none of that, saying: "I have listened to our fans about what happened in Athens, and it's a big blow we didn't bring the trophy home - but you've got to move on in football.
"We have to look now at our goals and dreams for this year, and that's to win more trophies.
"Everyone knows the Premier League is the priority but if we can go a long way in the European Cup again it would obviously be great for the club and the fans.
"Athens can be a spur. It was a big blow for everyone involved but good players and big clubs bounce back - you only have to look at AC Milan and how many finals they've reached over the years.
"We've got to use their attitude. They lost to us in the Istanbul final a couple of years ago but bounced back to win in Athens. Who's to say we can't do the same?"