Jones, who has won 30 caps, is one of the four captains in National Coach Steve Hansen's squad for the 2003 Rugby World Cup in Australia in October.
The 25-year-old becomes the eighth player to captain Wales since the turn of the millennium, following David Young, Scott Quinnell, Andy Moore, Colin Charvis, Jonathan Humphreys, Martyn Williams and Gareth Thomas.
The only survivor from the starting line-up against Ireland last Saturday is wing Gareth Thomas as Hansen rings the changes in the second of Wales' four-match World Cup preparation programme.
There are, however, 12 of the side who lined up against New Zealand at Waikato Stadium in Hamilton on 21 June who play against Clive Woodward's team, as well as lock Chris Wyatt who came on as a replacement in the 55-3 defeat.
The pair who missed the All Blacks encounter but are on duty on Saturday are Thomas - now just two short of Ieuan Evans' national record of 33 tries - and New Zealand-born centre Sonny Parker.
Wales follow Saturday's clash with matches against Romania at the Racecourse Ground in Wrexham on Wednesday (7.05 pm) and Scotland at the Millennium Stadium a week Saturday (2.30 pm).
Wales (v England): R Williams (Cardiff Blues); M Jones (Llanelli Scarlets), M Taylor (Llanelli Scarlets), S Parker (Celtic Warriors), G Thomas (Celtic Warriors); S Jones (Llanelli Scarlets, captain), G Cooper (Celtic Warriors); I Thomas (Llanelli Scarlets), R McBryde (Llanelli Scarlets), G Jenkins (Celtic Warriors), R Sidoli (Celtic Warriors), C Wyatt (Llanelli Scarlets), C Charvis (Unattached), M Williams (Cardiff Blues), D Jones (Llanelli Scarlets).
Replacements: G Williams (Cardiff Blues), A Jones (Neath-Swansea Ospreys), J Thomas (Neath-Swansea Ospreys), G Thomas (Neath-Swansea Ospreys), M Phillips (Llanelli Scarlets), T Shanklin (Cardiff Blues), G Henson (Neath-Swansea Ospreys).