Wednesday night sees interim Blues boss Benitez return to the competition where he made his name in England for what could be one match only.
The game which proved the final straw for Roman Abramovich in the rein of Roberto Di Matteo - the 3-0 defeat at Juventus 11 days ago - left Chelsea on the brink of becoming the first holders to crash out of the Champions League before Christmas.
Even if they secure the victory expected against Nordsjaelland in their final Group E match on Wednesday night, their campaign will be over if leaders Shakhtar do not beat Juve.
The Ukrainian champions have already qualified for the last 16 and need only a draw to hold on to top spot, a result that would also see Juve progress at Chelsea's expense.
Benitez said: "We know that a draw would be bad for us but the positive thing is that Shakhtar has a lot of good players and everybody is talking about them, so they have to show the rest of the world that they are really good players.
"When you know the top sides in Europe or in the world are watching you then you have to perform."
He added: "Obviously, Juve will go for the win but Shakhtar will need to show this level that they have."
While Shakhtar's players would not be forgiven for failing to give their all, their manager might be for fielding a weakened side in order to guard against the risk of injury.
But Benitez felt they would not risk surrendering top spot in the group, something which could land them a tougher draw.
He said: "They might finish second and have to play against one of the top sides in Europe and it will be more difficult, so I think they will try to win."
Benitez warned his players needed to focus on their own game against rock-bottom Nordsjaelland, pointing out their 4-0 win in the reverse fixture had flattered them.
He admitted keeping the Shakhtar v Juventus score from his squad would be almost impossible because the big screens and fans at Stamford Bridge would provide constant goal updates.
Benitez insisted Chelsea were not in as perilous a position as many have claimed and was confident they were good enough to become the first club ever to defend the Champions League - if they made it through.
The Spaniard went on to lift the European Cup with Liverpool eight years ago after they famously defied the odds in their final group game against Olympiacos.
In a match they needed to win by two clear goals, they scored twice in the final 10 minutes.
And while pointing out Chelsea's fate was not in their own hands, Benitez said: "If we go through, I can guarantee you there will be similar emotions."
The Blues will no doubt be branded "lucky" if they progress, having enjoyed outrageous fortune en route to last season's triumph.
Liverpool faced similar criticism in 2005.
"It's easy to talk but you have to be there, you have to win and Chelsea did it and Liverpool did it," said Benitez, who refused to criticise the the Blues' ultra-defensive tactics in Europe last season.
But he added: "I agree that sometimes the winner is not the best team."
Despite acknowledging Wednesday could be a one-off, the 52-year-old was looking forward to his first Champions League match for almost three years.
The man who famously outwitted the best coaches in Europe during his early years at Anfield said: "I like the challenge to play against the top sides and, obviously, the top sides have the top managers, so I like to challenge and to win and to compete."
And if Chelsea end up slipping into the Europa League?
"You have to win, or you try to win, every competition," he said.
"And if you play in the Europa League, you try to win the Europa League."