Williams is in line to make just his third start for his country when he lines up at Twickenham this Saturday.
The 31-year-old will win his eighth cap in total, some seven years after making his debut against France in 2003.
Williams starts ahead of Huw Bennett of the Ospreys after Scarlets star Matthew Rees was ruled out with a reoccurrence of a groin injury.
The former Bridgend No2, who has featured in six Magners League games so far this season, is joined in the starting line up by six more Blues, with Hook one of six Ospreys chosen by Warren Gatland in the Welsh XV.
British & Irish Lions tourist Hook will start at outside centre for the first time in an international when he lines up alongside fellow Lion Jamie Roberts.
Hook has previously played fly-half, inside centre and full back during his 37-cap career but this will be the first time he has worn the No13 shirt for his country.
Ospreys prop Adam Jones returns to the front row after missing the autumn internationals through a shoulder injury, while Blues wing Tom James gets the nod on the right wing ahead of clubmate Leigh Halfpenny who has to settle for a place on the bench.
Fellow Blue Richie Rees is in line to make his international bow after being named among the replacements for the first round of Six Nations action, while Lee Byrne starts at full back having had a two-week suspension overturned yesterday evening.
Wales squad to face England on Saturday, February 6 at Twickenham (kick-off 5pm)
15 Lee Byrne (Ospreys)
14 Tom James (Cardiff Blues)
13 James Hook (Ospreys)
12 Jamie Roberts (Cardiff Blues)
11 Shane Williams (Ospreys)
10 Stephen Jones (Scarlets)
9 Gareth Cooper (Cardiff Blues)
1 Gethin Jenkins (Cardiff Blues)
2 Gareth Williams (Cardiff Blues)
3 Adam Jones (Ospreys)
4 Alun-Wyn Jones (Ospreys)
5 Luke Charteris (Newport Gwent Dragons)
6 Andy Powell (Cardiff Blues)
7 Martyn Williams (Cardiff Blues)
8 Ryan Jones (captain) (Ospreys)
Replacements
16 Huw Bennett (Ospreys)
17 Paul James (Ospreys)
18 Bradley Davies (Cardiff Blues)
19 Jonathan Thomas (Ospreys)
20 Richie Rees (Cardiff Blues)
21 Andrew Bishop (Ospreys)
22 Leigh Halfpenny (Cardiff Blues)
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