Juventus vs. PSV (Tuesday, 5.45pm)
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Making their Champions League comeback after one year away, Italian giants Juventus host Dutch champions PSV Eindhoven on Tuesday evening.
On the opening matchday, the two-time winners will welcome 1988 victors PSV to Turin, as the clubs convene for their first competitive meeting.
We say: Juventus 2-1 PSV Eindhoven
While PSV are simply unstoppable on the domestic scene, Juventus have proven they will be tough to defeat under their new manager.
As a result, this could be a knife-edge encounter, with Juve's solid back line and wide range of attacking talent just tipping the balance in their favour.
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Young Boys vs. Aston Villa (Tuesday, 5.45pm)
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One of five teams making their Champions League debut this season, Aston Villa kick off their league phase campaign on Tuesday, as they visit Young Boys in Bern.
The clubs' first competitive meeting comes with Villa flying high in the Premier League and the hosts struggling at the start of their Swiss title defence.
We say: Young Boys 1-1 Aston Villa
With Barcelona next up for Young Boys - and Bayern Munich awaiting Aston Villa - the pressure will be on both sides to start with a win.
It may be a stalemate, though, as Villa are less convincing away from home and YB seem to be recovering from a sluggish start to the season.
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Bayern vs. Dinamo Zagreb (Tuesday, 8.00pm)
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Setting off on their 17th straight year in the Champions League, German giants Bayern Munich will welcome Dinamo Zagreb to the Allianz Arena on Tuesday evening.
The six-time European champions were knocked off their perch in the Bundesliga last season but have started brightly this term, while Dinamo claimed top spot again in Croatia and are back for another crack at the big time.
We say: Bayern Munich 3-1 Dinamo Zagreb
Bayern have won 20 of their last 25 Champions League home games, losing only once, so it is a daunting first-day trip for Dinamo to make.
Blessed with an abundance of in-form attacking options, the hosts can continue in that vein and put three points on the board straight away.
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AC Milan vs. Liverpool (Tuesday, 8.00pm)
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Old Champions League foes reunite in Tuesday's league phase opener, as AC Milan and Liverpool kick off their latest top-level European adventures under the bright lights of San Siro.
The two former continental champions will play their first Champions League games under new management this week, and both Arne Slot and Paulo Fonseca have some recent wrongdoings to rectify.
We say: AC Milan 1-1 Liverpool
Milan evidently benefitted from the two-week hiatus much more than Liverpool did based on their respective domestic displays, and the Rossoneri have also managed to avoid defeat in each of their last four Champions League games against English clubs.
Never before have the hosts gone five in a row without losing to a Premier League team in this competition, but we are backing that to change here, as any attacking alterations should only lead to limited success in front of goal for a wasteful Liverpool side.
> Click here to read our full preview for this match
> Two changes in attack? How Liverpool could line up against AC Milan
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> Will Chiesa finally play? Liverpool injury news for AC Milan clash
Sporting Lisbon vs. Lille (Tuesday, 8.00pm)
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Marking their first-ever Champions League meeting, Sporting Lisbon and Lille will convene at Estadio Jose Alvalade on Tuesday, kicking off the competition's new-look league phase.
While Portuguese champions Sporting are firing on all cylinders under Ruben Amorim, their visitors from France are still seeking consistency after a change of management.
We say: Sporting Lisbon 2-1 Lille
Sporting beat Lille twice in the Europa League group stage 14 years ago, and the clubs' first Champions League clash should go the same way.
Not only have the hosts suffered just one defeat in 28 league matches, they have won each of the last 19 on home soil: backed by a passionate fanbase, they are set to start the league phase with three precious points.
> Click here to read our full preview for this match
Real Madrid vs. Stuttgart (Tuesday, 8.00pm)
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Real Madrid and Stuttgart meet in the first matchday of the brand new league phase of the Champions League on Tuesday night.
In the first-ever meeting between the two sides, holders Real Madrid will look to make a perfect start as they begin their quest for title number 16.
We say: Real Madrid 3-1 Stuttgart
As reigning champions, Real Madrid will enter this opening day fixture as heavy favourites, and they should extend their unbeaten start to the season with a victory despite some possible absences in midfield.
CSKA Moscow six years ago are the only club to have stopped Real scoring in their last 74 home Champions League matches, so Stuttgart need to be on form in attack to have any chance here, and that looks unlikely given the might across the home squad.
> Click here to read our full preview for this match
> Will Bellingham recover in time? Real Madrid predicted lineup vs. Stuttgart
> Bellingham, Tchouameni back in training: Real Madrid injury list vs. Stuttgart