As well as wearing the armband in the absence of Scott Brown, the Greek international will carry the responsibility as the Parkhead club's top scorer in European competition.
Samaras has become a specialist at snatching vital goals on the road, but recognises this is an occasion when he needs to give the home crowd something to cheer.
He believes it is a big advantage that he spent four years learning his trade in Holland with Heerenveen before making a £6million move to Manchester City then transferring to Celtic where he has spent almost six years.
Sami knows what to expect tonight, and is happy to pass on this information to his less experienced team-mates.
"I know exactly how, not just Ajax, but how all teams play in Dutch football, and I don't think they are going to change anything just because they are playing at Celtic Park," said the 28-year-old, who will be starting his 60th European game and who has 15 goals to his credit.
"They try to pass the ball and play good attacking football, and try to win."
All of which Celtic will attempt to emulate, and Sami is anticipating another epic European night at a packed Celtic Park.
The fans and Celtic players will be hoping to enjoy a happier ending than last time, when Barcelona came to town and left with all three points.
Added to the defeat against AC Milan in the San Siro, it left the Hoops rooted to bottom spot in the group.
But Sami does not believe there is any reason to panic because Celtic have not been out of their depth in either game.
He reckons it needs only a marginal improvement, especially in front of goal, to bring them what they deserve.
Samaras said: "We lost the first two games to great teams on really small details.
"We made some mistakes and they cost us. Hopefully, we will be more focused, more competitive, and, of course, when we get chances, put them in the net."
If it's Sami who does the needful tonight, he will enhance an already impressive reputation.
Being the hero who kick-started their 2013-14 group campaign would also strengthen his position when he finally sits down to discuss a new contract to replace the one which is in its final year.
Not that the big man is in any way distracted by his employment status.
He is as happy as a sand Bhoy and, despite his scoring exploits bringing him to the attention of clubs across Europe, he has found his own Paradise, playing for Celtic under Neil Lennon.
"From day one when I came here he knew exactly my character and my strengths in a game," said Sami.
"The big problem I had years ago was consistency. He helped me so that week in, week out, I was playing well.
"I wasn't going from high to low and then low to high. I found a balance in my game.
"When there is full understanding between a player and a manager, that makes it easier for everyone."
Now Samaras is happy to be one of Lennon's most trusted lieutenants, especially on big occasions like tonight.
He said: "I always try to explain to other people, but there are no words to express the atmosphere in the stadium on Champions League nights.
"It's everything, from the warm-up, the Champions League anthem, during the game, after the game."