Having made a try-scoring impression from fullback last weekend against England, Daly is starting at outside centre, while up front Marco Wentzel starts at lock and Sam Jones starts at openside flanker.
Other changes see Nick Evans, Sergio Parisse, Dmitri Yachvili and Martin Castrogiovanni among the internationals called into the side following the 40-12 loss to England at Twickenham.
Parisse will captain the team with former All Black Joe Rokocoko starting on the wing. Parisse and Jones are joined by Northampton's Samu Manoa in the back row, while Dean Mumm, Castrogiovanni, Schalk Brits and Paul James all start.
Kahn Fotuali'i and Leonardo Ghiraldini have been added to the bench.
The match will be the second time the Lions have played the Barbarians, with the iconic sides having clashed in 1977 as part of the Queen's Silver Jubilee celebrations. The Lions won that match 23-14.
The Barbarians are led by Wasps Director of Rugby Dai Young who said he expected a much stronger performance this weekend.
"We all felt a little bit let down last weekend. We didn’t play anything like how we expected to play and we know we have to be a lot better. The preparation has been a lot better for this game and the players themselves realised that they have to step up this week."
Barbarians: 15 J Payne, 14 J Rokocoko, 13 E Daly, 12 C Laulala, 11 T Ngwenya, 10 N Evans, 9 D Yachvili, 1 P James, 2 S Brits, 3 M Castrogiovanni, 4 M Wentzel, 5 D Mumm, 6 S Manoa, 7 S Jones, 8 S Parisse.
Replacements: 16 L Ghiraldini, 17 D Jones, 18 J Hamilton, 19 I Harinordoquy, 20 A Lo Cicero, 21 K Fotuali'i, 22 J Hook, 23 M Tindall