It completes an outstanding rise for the Brighton centre-half, who only made his debut from the bench in the Three Lions' 1-0 friendly win over Austria at the Riverside Stadium on Wednesday - and followed up with his first start in the single-goal victory over Romania in Middlesbrough on Sunday - where he produced a solid performance.
White has been chosen ahead of York-born defender Ben Godfrey, winger Jesse Lingard, forward Ollie Watkins and midfielder James Ward-Prowse, with the latter making his pitch for inclusion with a strong performance in the triumph over the Romanians on Teesside.
But Poole-born White, who can operate across the backline, has been given the nod and will provide invaluable cover in defence, where England still have a big injury concern regarding Harry Maguire, who has been out for a month with ankle ligament damage and is set to miss the Group D opener with Croatia at Wembley next Sunday.
Speaking after the win over Romania on Sunday and discussing whether the performance of Ward-Prowse had been potentially fateful, Southgate was circumspect and said that his decision would be based not on friendly form, but positional concerns.
He said: “Prowesy’s professionalism and approach all week, given the disappointment of being left out has been absolutely first-class.
“The decision will not necessarily be about the performances today as such. It is going to be positional really and the area we feel we might need the most cover.
“I could not have been happier with the way Jeese (Lingard) and Oli Watkins approached things and the two young defenders (Ben White and Ben Godfrey).
"They have all had excellent weeks and their mentality is what we have expected from the group.”
Being named in the squad caps an impressive first season in the Premier League for White, who was recently named as Brighton's Player of the Season.
White had previously enjoyed an outstanding campaign on loan at Leeds in helping the Elland Road club win the Championship title in 2019-20 and earning a place in the Championship Team of the Year.
Gareth Southgate’s squad will continue their tournament preparation at St. George’s Park this week ahead of the opener with the Croats next weekend.
England squad: 1. Jordan Pickford, 2. Kyle Walker, 3. Luke Shaw, 4. Declan Rice, 5. John Stones, 6. Harry Maguire, 7. Jack Grealish, 8. Jordan Henderson, 9. Harry Kane, 10. Raheem Sterling, 11. Marcus Rashford, 12. Kieran Trippier, 13. Dean Henderson, 14. Kalvin Phillips, 15. Tyrone Mings, 16. Conor Coady, 17. Jadon Sancho, 18. Dominic Calvert-Lewin, 19. Mason Mount, 20. Phil Foden, 21. Ben Chilwell, 22. Ben White, 23. Sam Johnstone, 24. Reece James, 25. Bukayo Saka, 26. Jude Bellingham.