The Spaniard managed Tottenham for a year from 2007 to 2008, going on to coach Real for a short spell in 2008-09 as well after he was sacked by the north London club.
"It’s a very special match," the 63-year-old told Goal ahead of Tuesday's meeting between the two teams at the Santiago Bernabeu. "I think Tottenham have grown a lot since I was there. Both matches, the Wembley one and the game in Madrid, will be very special and even.
"I think that at the moment, Madrid are possibly a level above Spurs. They are European champions, they are at a very high level. I think second place [in the group] will be between Tottenham and Borussia Dortmund. They will have to fight it out, but within the group I would say that Real Madrid are the favourites."
Real Madrid are in much better shape than when he was at the club, while Spurs have come third and second in the Premier League over the past two seasons — their best finishes in decades. So is he happy to see his former sides doing so well?
"Yes, of course," he said. "You enjoy the situation they are experiencing because you are fond of them due to the time you have spent with them and you always leave friends within the club."
Despite Tottenham's growth and improvement under Mauricio Pochettino, the north London club are yet to add any silverware with the Argentine coach and, remarkably, Ramos remains the last Spurs boss to win a trophy — the League Cup in 2007-08.
"It was something that was talked about a lot over there," he said. "When I arrived, they had gone many years (since 1999) without winning a trophy and they always said that is what they most wanted, what excited them most was winning a trophy. And thanks to God, we achieved that. Now, almost 10 years have gone by and they haven't won another title. I hope they don't have to wait too much longer."
After that triumph, however, things took a turn for the worse for Ramos at White Hart Lane as the team picked up just two points from their first eight Premier League games in 2008-09 and he was replaced by Harry Redknapp.
Nevertheless, the Spaniard believes the sales of Dimitar Berbatov and Robbie Keane over the previous summer left him in a precarious position, one from which he was unable to recover.
"I always say that the problem I had at Tottenham that season was that, on the last day of the transfer window, they sold Berbatov, and a few days before they sold Robbie Keane," he said. "And the window closed without the possibility of signing replacements.
"We ended up without any strikers, the only striker there was Darren Bent. And we weren't strong enough to save the season. In fact, in the next window, they spent £50 million to solve the problem…"
And on Real's rise over the past few seasons, he said: "This is cyclic. Those footballers that were spectacular for Barcelona, like Xavi, he's not there, [Andres] Iniesta is getting older. Those footballers, either they have lost some of their physical condition, or more of them have left. And now, Real Madrid are on the crest of a wave."
Before the arrival of Jose Mourinho as Madrid coach in 2010, Los Blancos were knocked out in the last 16 of the Champions League for six seasons in a row. However, Real have reached the semi-finals every year since and won the trophy three times — twice under Zinedine Zidane.
"His numbers are spectacular," Ramos said. "He came out of Castilla to coach Real Madrid. He had a year as assistant to [Carlo] Ancelotti as well and I think that helped him.
"As a player he experienced all kinds of situations and now he is at a team that is among the best in the world. He has had spectacular results and he is managing the squad with a lot of intelligence."