The Reds travel to Edinburgh to face the Scottish side in the Europa League after comfortably dispatching FC Gomel 4-0 on aggregate, while Hearts were thumped 5-0 by Tottenham at this stage last season.
Rodgers' honeymoon period with the club was over inside 90 minutes at the Hawthorns on Saturday though, as the Reds slumped to a 3-0 defeat at the hands of Steve Clarke's West Brom side.
But Rodgers says his players have responded well in training.
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"It's certainly something that I've noticed in my short time here, that they are allergic to complacency," he told reporters.
"There is no question about that. They focus every day and their concentration is good. They'll understand the size of the task in terms of coming here and having to play well."
The Scottish club haven't brought in any new signings in spite of a huge clearout at Tynecastle amidst sweeping cutbacks, but the new boss at Anfield believes John McGlynn's side will be looking to make amends for last season's disappointment against Spurs.
He added: "I think Hearts will be better for that experience. They might have some regrets from last year.
"The game was over early on and it left them with an uphill task going forward. I'm sure they will be right up for this game."
Rodgers has only been able to bring in two fresh faces on Merseyside since his arrival from Swansea, signing midfielder Joe Allen and former Swan Fabio Borini from Roma.
Daniel Agger was dismissed by Phil Dowd for a professional foul on Shane Long at the weekend, and with a fairly small squad Rodgers also revealed that the Europa League is the perfect opportunity to blood some of the club's youngsters.
"We've got a very small squad to be fair so I've got to try to protect some of the players," he added.
"We played for over half an hour with 10 men on Saturday as well and we've got a massive game at the weekend.
"I trust my players, I trust the group and whatever team we put out will always be to win the game.
"We want to do well in the competition but it's a great opportunity for me to see the young players mixed in along with some of the experienced players."
Kenny Dalglish clinched the League Cup and reached the FA Cup final last season, but was dismissed at the end of the campaign after finishing eighth in the Premier League. Liverpool finished four points below neighbours Everton in a disastrous season, which saw them beaten on four occasions in the league at Anfield.
And despite defeat on the opening day, Rodgers confirmed that the league was the club's main priority.
He added: "Our main objective is the league - there is no question about that.
"When you work at Liverpool - whether as a player or manager - every game is important.
"It's a very important game for us, we want to do well. The objective over the two games is to get through to the group stages.
"It's certainly a game we want to win and we want to qualify over the course of the two games. We will pick strong teams that we think can do that."