Youngs is one of seven Tigers players in head coach Stuart Lancaster’s matchday squad, including his brother Ben, who is named among the replacements.
Tom, who played twice in midweek during the summer tour to South Africa, will start alongside Tigers team-mate Dan Cole and Harlequins prop Joe Marler.
Geoff Parling and Thomas Waldrom start in the pack and Manu Tuilagi partners Brad Barritt at centre. Toby Flood, the most experienced player in the squad, starts at fly-half for his 51st cap with Danny Care at scrum-half.
There are five changes to the starting XV from the final Test against the Springboks, including Charlie Sharples coming on to the right wing for Chris Ashton and Ugo Monye taking over from Ben Foden on the left. Chris Robshaw returns as captain at open-side flanker for James Haskell.
Mako Vunipola (Saracens) and Joe Launchbury (London Wasps) are set to make their England debuts from the bench.
Lancaster said: “Congratulations to Tom Youngs, who has made a great transition from centre to hooker in a short period and deserves his chance, as do Joe Launchbury and Mako Vunipola, who we are pleased to be able to include in the squad.”
England (v Fiji, 2.30pm Saturday, Twickenham Stadium, Sky Sports HD)
15 Alex Goode (Saracens, 2 caps)
14 Charlie Sharples (Gloucester Rugby, 2 caps)
13 Manusamoa Tuilagi (Leicester Tigers, 13 caps)
12 Brad Barritt (Saracens, 7 caps)
11 Ugo Monye (Harlequins, 13 caps)
10 Toby Flood (Leicester Tigers, 50 caps)
9 Danny Care (Harlequins, 33 caps)
1 Joe Marler (Harlequins, 3 caps)
2 Tom Youngs (Leicester Tigers, 0 caps)
3 Dan Cole (Leicester Tigers, 31 caps)
4 Tom Palmer (London Wasps, 40 caps)
5 Geoff Parling (Leicester Tigers, 8 caps)
6 Tom Johnson (Exeter Chiefs, 3 caps)
7 Chris Robshaw (Harlequins, capt, 8 caps)
8 Thomas Waldrom (Leicester Tigers, 2 caps)
Replacements
16 David Paice (London Irish, 2 caps)
17 David Wilson (Bath Rugby, 19 caps)
18 Mako Vunipola (Saracens, 0 caps)
19 Joe Launchbury (London Wasps, 0 caps)
20 Tom Wood (Northampton Saints, 9 caps)
21 Ben Youngs (Leicester Tigers, 24 caps)
22 Owen Farrell (Saracens, 8 caps)
23 Mike Brown (Harlequins, 7 caps)
