The two sides take each other at 7pm GMT in Volgograd after Group G rivals Belgium and Panama have battled it out in Sochi.
The Red Devils are the favourites to qualify from the group in Russia at 1/12, but England are not far behind at 1/9, while Tunisia (9/2) and Panama (10/1) are huge outsiders.
Those expectations of qualification have also been reflected in the odds handed to Gareth Southgate's men for their opening clash.
SkyBet have the Three Lions at 4/9 to beat Tunisia, while the opposite result is on offer at 15/1.
The draw is priced at 10/3 at the same bookies.
In the first scorer market, Harry Kane leads the list at 2/1, followed by Jamie Vardy (5/2), Marcus Rashford (3/1) and Danny Welbeck (7/2).
Fakhreddine Ben Youssef, Saber Khalifa and Wahbi Khazri are at the shortest odds to score for Tunisia, with all three at 10/1.
In the other Group G clash, Belgium are 2/11 to claim victory over Panama hours before England's tournament bow.
A Panama upset is at 16/1, while the draw is available at 11/2.