He would atone for that by reaching the semi-final with Monaco a few years later but in his six years in Glasgow there was nothing but disappointment. Collins' stint as a Celtic player came slap-bang in the middle of an era of Rangers dominance as the Ibrox club went on to match Celtic's record by claiming nine successive championships.
Only in 1997, a year after Collins had moved on to the south of France, did Uefa open up their flagship club competition to include teams who hadn't just won their domestic title, meaning Rangers were Scotland's sole Champions League representative for most of the 1990s, albeit with limited success.
That remains a source of regret for Collins, but another chance to represent Celtic in European football's most prestigious competition has now presented itself. The new assistant to manager Ronny Deila will watch with professional interest as Scotland's European representatives discover their fate tomorrow when the draw for the first and second qualifying rounds of both the Champions League and Europa League is made in Nyon.
"It's a regret when I look back and see that I didn't get the chance to play in the Champions League with Celtic," he said. "But you can't get everything you want in life. It'll be great for me to be able to coach in the Champions League.
"It'll be fantastic to pit your wits against the big boys as it's where we want to be."
Celtic must first find a way through three potentially tricky qualifying rounds before they can daydream about taking on Europe's elite. They passed a similar challenge last season but it wasn't without its moments. Northern Ireland's Cliftonville were dispatched with minimal difficulty in the second qualifying round but Elfsborg of Sweden and then Kazakhstan's Shakhter Karagandy in the subsequent rounds both posed far greater tests.
Celtic should again be seeded in each of their three qualifying ties this time, although they play the first two home matches at Murrayfield with Celtic Park unavailable due to the Commonwealth Games.
Travel difficulties will likely be kept to a minimum in the second qualifying round, with Uefa set to announce - probably tomorrow morning - smaller, regionalised pots ahead of the draw. That could see Celtic play another side from the British Isles - St Patrick's Athletic from the Republic of Ireland, Wales' The New Saints, and Cliftonville are all in the unseeded half - while Scandinavian sides, including Deila's old club Stromsgodset, could also be considered "local".
With the opening match in mid-July and the team back for pre-season training on Tuesday, there isn't a huge amount of time for the new management team to get the players ready.
"It's early in the season so there's not a lot of preparation," Collins said. "But that has been the case for the last few years so we know what's coming. We just have to make sure that on Tuesday we get the work started and are ready for the big games. These are massive games even though they might not be against massive clubs. We will just have to wait to see who we are going to face but like every football match, it'll be what we do that counts."
Collins' most recent exposure to the Champions League came from a seat in the Sky Sports studios. The former Scotland international was an analyst for the TV station on the big European nights and so watched many of Celtic's matches over the last few seasons. With the majority of last year's squad set to return for the new campaign, it gives Collins hope that the team can again make an impact in the competition.
"There have been some excellent performances," he said. "You have the jump up from the Premiership to the Champions League and it's a big jump. But Celtic have proved they can get the results and it's been big results. It's a challenge for myself and the manager as we need to get the players ready, but we have a terrific squad."
Both Deila and Collins are idealists rather than pragmatists when it comes to how the game should be played. The prospect of "parking the bus", even in a European away game, is anathema to the Scot.
"Not from kick off, I would never do that, If you are 1-0 up with five minutes to go, then you'll park the bus to get the result. I'll always want my teams to dominate the game and control the ball. That'll never change. I'll always want that and I'll always work towards that on the training pitch.
"The reality is that in some games you won't be able to do that. You go up against better teams and better players and they will have more of the ball.
"But what we will never stop is working on the training park to go up against them and keep the ball. We'll try to create chances and score goals. My mindset and methods in training and coaching will never change."