Munster's Simon Zebo, who joined the tour party on Tuesday, will make his Lions debut against the Waratahs.
His Ireland colleague Rob Kearney will make his first appearance of the tour on the bench after recovering from a torn hamstring that made him unavailable for selection until this point of the tour.
Also joining Zebo in the starting line-up are fellow Ireland internationals Paul O'Connell, Jonathan Sexton and Jamie Heaslip, the latter pair notably facing a side coached by their former Leinster boss Michael Cheika. O'Connell's ex-Munster coach Alan Gaffney is also part of the Waratahs coaching set-up.
British & Irish Lions tour manager Andy Irvine said: "The tour has now moved on to Sydney where we face another tough examination in front of a parochial sell-out crowd. The squad has a lot of respect for the Waratahs who have proven down the years to be tough opponents.
"The match represents the final Saturday match prior to the first Test in Brisbane. Naturally, the players know that Test places are still up for grabs and they will be eager to press for selection against the Wallabies."
Head coach Warren Gatland said: "It would be great to remain unbeaten and take that momentum into the first Test. However, more importantly we are looking to finalise key playing combinations and strengthen our patterns of play during the next two matches.
"This match, the fourth of our lead-up matches in Australia, will assist in this process. To beat the Waratahs we know we have to improve on our strong performance last Saturday against the Reds. This side is more than capable of doing that."
BRITISH & IRISH LIONS Team & Replacements (v NSW Waratahs, 2013 British & Irish Lions Tour, Allianz Stadium, Sydney, Saturday, June 15, kick-off 7.40pm local time/10.40am Irish time):
15. Leigh Halfpenny (Cardiff Blues/Wales)
14. Sean Maitland (Glasgow Warriors/Scotland)
13. Jonathan Davies (Scarlets/Wales)
12. Jamie Roberts (Cardiff Blues/Wales)
10. Jonathan Sexton (Leinster/Ireland)
9. Mike Phillips (Bayonne/Wales)
1. Mako Vunipola (Saracens/England)
2. Tom Youngs (Leicester Tigers/England)
3. Adam Jones (Ospreys/Wales)
4. Alun Wyn Jones (Ospreys/Wales)
5. Paul O'Connell (Munster/Ireland)
6. Tom Croft (Leicester Tigers/England)
7. Sam Warburton (Cardiff Blues/Wales) (capt)
8. Jamie Heaslip (Leinster/Ireland)
16. Richard Hibbard (Ospreys/Wales)
17. Alex Corbisiero (London Irish/England)
18. Dan Cole (Leicester Tigers/England)
19. Geoff Parling (Leicester Tigers/England)
20. Dan Lydiate (Newport Gwent Dragons/Wales)
21. Ben Youngs (Leicester Tigers/England)
22. Owen Farrell (Saracens/England)
23. Rob Kearney (Leinster/Ireland)