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.
Match preview
For the unprecedented 15-time Champions League winners, Real Madrid will begin the new campaign at the Santiago Bernabeu, three months after beating another German club in the final.
June's final saw Carlo Ancelotti's men beat Borussia Dortmund 2-0 at Wembley, resulting in Los Blancos' sixth crown in 10 years.
Stuttgart are the side they will begin against this time around, becoming the 16th different German side Real have faced in the competition.
Real faced four clubs from Germany on their road to London last season, playing Union Berlin in the groups, RB Leipzig in the last 16 and juggernauts Bayern Munich in the semi-finals.
The hosts will be glad of playing another here, as Real's record against German opposition is excellent in the Champions League, losing just one of their last 21 - winning 14.
While it was a 2-0 win that sealed the cup last season, Ancelotti's side come into this game on the back of a victory by the same scoreline at the weekend, in an impressive performance away to Real Sociedad, extending their unbeaten start to six games this season in all competitions, even though they remain four points behind Barcelona in La Liga.
Based on the UEFA coefficient, Real got one of the kinder draws for the league phase, but Stuttgart are, on paper, one of the toughest pot four sides in the competition.
The holders will also welcome Dortmund to the Bernabeu in a repeat of last season's final, while they also must travel to face Liverpool and Europa League winners Atalanta.
On the contrary, Stuttgart have been handed one of the toughest draws, largely due to the fact they must face Real Madrid away to begin their campaign.
The Swabians will also go to Juventus, and host Paris Saint-Germain and Atalanta in what is their first Champions League campaign for 15 years.
Stuttgart are winless in their six meetings against Spanish opposition in the UCL, drawing two and losing four, including their last game in the competition back in March 2010, when Barcelona beat them 4-0 to knock them out at the last 16 stage.
Last season's Bundesliga runners-up did feature in the Europa League later down the line, but this is still their first European match since losing a qualifier to Rijeka in 2013.
The visitors will come into the game with some confidence though, after Sebastian Hoeness's men beat Borussia Monchengladbach 3-1 at the weekend to make up for an underwhelming start.
That was their first league win of the season, after losing on the opening day to Freiburg and drawing at home to Mainz, as they sit in mid-table on four points.
Real Madrid form (all competitions):
W
D
W
D
W
W
Stuttgart form (all competitions):
Team News
Kylian Mbappe is set to make his Champions League debut for Real Madrid here, after scoring 48 goals in 73 appearances in the competition for PSG and Monaco.
Around the Frenchman though, Real remain quite light on numbers ahead of this clash, as a number of key first-team player have been out with injury, meaning they have struggled to name a full bench in recent weeks.
Jude Bellingham is the most notable after missing the last month of action, but he is back in training along with Aurelien Tchouameni, after both missed the recent international break.
Brahim Diaz was forced off early at the weekend and is set to be out for around eight weeks with a muslce injury, while Eduardo Camavinga and Dani Ceballos are set to be back at the end of the month.
Ameen Al Dakhil is yet to make his Stuttgart debut as he recovers from an injury suffered at his time with Burnley, but fellow defender Leonidas Stergiou is closing in on a return from a back issue.
Nikolas Nartey and Frans Kratzig are not likely to return until October, while youngster Justin Diehl will be out for even longer after picking up a shoulder injury playing for the B team.
Stuttgart's best chance of success will lie with their attackers, and Ermedin Demirovic is in red-hot form with five goals already this season for club and country, after netting two at the weekend.
Deniz Undav also found the net at Gladbach, grabbing his first league goal of the campaign after starring for Germany against Holland during the international break.
Real Madrid possible starting lineup:
Courtois; Carvajal, Eder Militao, Rudiger, Mendy; Valverde, Modric; Rodrygo, Bellingham, Vinicius Junior; Mbappe
Stuttgart possible starting lineup:
Nubel; Vagnoman, Chase, Chabot, Mittelstadt; Leweling, Karazor, Stiller, Rieder; Demirovic, Undav
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.