The 54-year-old will eclipse Spaniard Rafa Benitez, Dutchman Ronald Koeman and Italian compatriot Claudio Ranieri, who have all coached five sides in Europe's elite club competition, when he takes charge of Real in Tuesday's Group B opener against Galatasaray in Istanbul.
"I have a special feeling about becoming the first man to coach six different sides because this is the most important competition in the world," Ancelotti told a news conference in Istanbul on Monday.
"It is also exciting because it will be my first match coaching Real Madrid (in Europe) and everyone knows we want to win the Cup although it will not be easy," he added.
"The fact that I will be involved in this is a fantastic motivation for me."
Ancelotti enjoyed a winning Champions League start with all his previous teams - Parma, Juventus, AC Milan, Chelsea and Paris St Germain - and won the competition with Milan in 2003 and 2007.
He took over at Real from Portuguese Jose Mourinho at the end of last season, charged with securing the 10th European crown the big-spending Spanish giants have been chasing since their last triumph in 2002.
Tuesday's game is also likely to mark Gareth Bale's Champions League debut for Real after the Wales winger joined from Tottenham Hotspur for a world record fee of €100 million (£86) this month.
Bale scored on his first appearance in La Liga in Saturday's 2-2 La Liga draw at Villarreal, when Real dropped their first points of the campaign.
Real's massive outlay on the 24-year-old, which broke the previous record of €94 million (£80m) the club paid Manchester United for Portugal winger Cristiano Ronaldo in 2009, has prompted criticism in Spain, which is in the grip of a punishing recession and suffering from painfully high unemployment.
Ancelotti said he and the players were not distracted by transfer dealings and were focused on their jobs.
"I think the financial issues, the big transfers are stories for the newspapers and television but not for us," he said.
"Everyone in the team is focused on training well and winning, and nothing else."
Ancelotti confirmed goalkeeper Iker Casillas would start Tuesday's game instead of Diego Lopez, in line with his policy of playing Lopez in La Liga and Spain captain Casillas in European competition.
"Casillas and Diego are both very good goalkeepers and the competition between the two makes both of them better," the Italian added.
"Casillas's huge experience in the Champions League makes him my first choice.
"He has everything he needs to put up with the pressure, he has no problem.
"For now, Diego will keep playing in the league and Casillas will continue to be our Champions League keeper."