Holders Real Madrid are among the headline acts on the opening night as they host Stuttgart at the Estadio Santiago Bernabéu.
Los Blancos beat Borussia Dortmund 2-0 in last season's final and defeated Real Sociedad by the same scoreline on Saturday.
It could be a similar story against Stuttgart, who triumphed 3-1 at Borussia Monchengladbach on Saturday and look to be finding their feet after losing some of their best players over the summer.
Sebastian Hoeness will relish the test against Carlo Ancelotti, but while his side's all-action style means they could have positive moments in Madrid, the Italian's nous is typical of his team.
Despite their star-studded line-ups over the last decade, Real Madrid's UEFA Champions League success has been built on frustrating opponents and grinding out results - that could be the case again on Tuesday.
Real Madrid to win 2-0 - 15/2
It seems somewhat curious to kick off with a correct scoreline prediction, but 2-0 is a result that has followed Real Madrid around.
The holders beat Sociedad by that score after doing the same to Real Betis before the international break. It was also the outcome in June's UEFA Champions League final win over Borussia Dortmund at Wembley.
Stuttgart return to the UEFA Champions League for the first time since 2009/10 when they lost to Sevilla in the group stages before being defeated by Barcelona in the round of 16.
Die Roten finished second in last season's Bundesliga, but lost key players such as Hiroki Ito, Waldemar Anton and Serhou Guirassy, although they have signed Deniz Undav on a permanent deal and acquired Ermedin Demirović.
Those are solid signings but Real brought in Kylian Mbappé. The Frenchman scored a penalty at Sociedad, as did Vinícius Júnior, but those two are still to truly click and Ancelotti's side are not exactly blowing sides away.
The hosts are 6/4 to win to nil, but backing 2-0 adds additional value and it would be little surprise to see them gain a result in characteristically grinding fashion.
Real Madrid to score a penalty - 3/1
Real Madrid have scoring four penalties in their last three games and Los Blancos could make that five against Stuttgart.
The fact they have some of the best dribblers in the game often means their front line are dangerous to challenge around the box and Ancelotti's side might be worth backing to score another spot-kick.
Stuttgart have already conceded a penalty this term, doing so in their 3-3 draw against Mainz and there were also two penalties scored in the first leg of Los Blancos' UEFA Champions League semi-final first-leg draw against Bayern Munich in April.
Both goals against Sociedad resulted from penalties. Each decision may have gone a different way, but were prompted by poor defending and the hosts could score from the spot again.
Josha Vagnoman to be booked - 9/2
With Mbappé, Vinícius and Rodrygo all naturally drifting to the left, the right edge of the Stuttgart defence could be busy and right-back Josha Vagnoman could go into referee Umut Meler's notebook.
The 23-year-old has been booked in both of his Bundesliga outings this season.
There is uncertainty over whether he will start, but his first yellow of the campaign came off the bench against Mainz, before he was also being cautioned after starting the win at Borussia Monchengladbach.
Vagnoman was only booked twice last season, but missed the end of the campaign with a foot injury and still appears to be working towards full fitness.
Even so, he should get minutes and another yellow card could be in the offing.
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Real Madrid - 2/7
Draw - 5/1
Stuttgart - 17/2
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This article was written by a partner sports writer via Spotlight Sports Group. All odds displayed on this page were correct at the time of writing and are subject to withdrawal or change at any time.
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