The two international powerhouses head Group F - widely dubbed the 'Group of Death' - with Portugal taking on Hungary earlier in the day.
Didier Deschamps's star-studded Les Bleus are out to add to their 2018 World Cup triumph by claiming the European crown - with Kylian Mbappe and Antoine Griezmann heading a squad brimming with talent.
As for Germany, their head coach Joachim Low will step down as coach at the end of the tournament, and will be hoping to bow out on a fitting note.
The match may be being played at the Allianz Arena, but that should not deter France as they bid to add another international trophy to their already impressive cabinet.
Today's the day :grin::raised_hands:
Our @EURO2020 campaign finally gets underway tonight against none other than world champions France! :flag_fr::flag_de:#DieMannschaft #GER #EURO2020 #FRAGER pic.twitter.com/eJDZZjCrIr
- Germany (@DFB_Team_EN) June 15, 2021
Les Bleus are unbeaten in their last five games against Germany, while they have lost only two of the previous 13 in the head-to-head.
With this summer's tournament now in full swing, our tipster Robert Mann takes a look at some of the best bets from France vs Germany to get your teeth stuck into.
Hungary vs Portugal betting tips & predictions
France are 13/8 to win, with Germany priced at 13/8 to come away with the victory. A draw is priced at 23/10.
Prediction: 1-0 (14/1)
Half-Time/Full-Time: Draw/France (5/1)
France come into this tournament as favourites after lifting the World Cup three years ago, as well as finishing runners-up at the last European Championship back in 2016.
Germany, meanwhile, arrive with confidence at an all-time low - especially after their shock 2-1 defeat to North Macedonia in March during a World Cup qualifier.
As well as their World Cup 2018 failure, the three-times Euros winners have since recorded just two victories from ten UEFA Nations League fixtures.
They even suffered a heavy 6-0 defeat to Spain in their final match last November.
We think both teams could start off slow, with France taking full control in the second half.
First goalscorer: Kylian Mbappe (11/2)
Having also come unstuck 2-1 at home to North Macedonia in their most recent World Cup qualifier back in March, it is hard to see the Germans handling a France side that has looked extremely dominant in recent years.
We expect Mbappe to take full advantage of Germany's poor run of form and will, almost certainly, be a contender for the Golden Boot at this summer's showpiece.
Request A Bet: Benzema, Mbappe & Werner 1+ shots on target each (6/5)
Timo Werner has been known for firing blanks as of late for Chelsea, but tends to be a different player in a Germany shirt.
For that reason, we reckon the trio of forwards to all have one or more attempts on goal looks a solid bet for this evening's heavyweight clash.
Odds are correct at the time of publication and are, as always, subject to change.
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France team news
A feud between strikers Kylian Mbappe and Olivier Giroud has gone public, threatening team unity before their big match against Germany.
It began on Tuesday after France's 3-0 victory against Bulgaria in a friendly when Giroud suggested he was not getting the service he deserved - considered by some to be a swipe at Mbappe.
:100:% Focus :punch: pic.twitter.com/Tp7NevObsv
- French Team :star::star: (@FrenchTeam) June 13, 2021
In terms of team news, it remains whether or not Deschamps will decide to pick the recently recalled Karim Benzema ahead of World Cup winner Giroud. It is believed that he will.
Other than that, Les Blues boast a fully-fit squad to choose from.
Germany team news
It remains to be seen, however, whether there is enough room for Chelsea pair Kai Havertz and Timo Werner.