Donncha O'Callaghan becomes the third Magners League player to captain the Lions in 2009, following in the footsteps of fellow Irish internationals Paul O'Connell and Brian O'Driscoll, as well as England prop Phil Vickery.
A further four Magners League players have been named among the replacements, taking the matchday total to 13.
Selection for this weekend's first international against South Africa will not be decided until after Tuesday's night clash at the Nelson Mandela Bay Stadium, meaning the likes of Keith Earls, Luke Fitzgerald and Andy Powell will have one last chance to push for a place in Ian McGeechan's first-choice XV.
Leinster centre Gordon D'Arcy makes his first start of the tour having joined the party late to provide midfield cover, while Ospreys fly-half James Hook has the chance to build on Saturday's heroics against Western Province.
The 23-year-old kicked a stunning 50-metre penalty to keep the Lions' 100-per-cent winning record intact in Cape Town and will now be looking for an equally impressive contribution for a full 80 minutes.
"This is Test week and there is a noticeable change in attitude within the touring party," said McGeechan.
"We are now heading towards the business end of the tour and the reason why we have come to South Africa.
"As you would expect, the immediate focus is the next match against the Southern Kings on Tuesday before attention turns to selection for the First Test for which all players will be considered.
"The Southern Kings are not a regular team but we understand there are some very talented players in the squad for the match. Experience tells me that you can never underestimate any South African team and like the other teams we have faced on the tour so far we will not take them lightly.
"Seven players are backing up from the Western Province match with Nathan Hines, Joe Worsley, Riki Flutey and Keith Earls given the opportunity in the starting XV in different positions.
"The team will be captained by proud Munster man Donncha O'Callaghan, an experienced Lions tourist, who is a very popular member of the squad. This will be his 10th Lions match including two Tests against New Zealand during the 2005 tour.
"As mentioned by doctor Gary O'Driscoll yesterday at our medical briefing we will give Mike Blair a fitness test on Tuesday morning. He had to withdraw from the replacements bench against Western Province last Saturday due to a foot injury."
British & Irish Lions vs Southern Kings
15. Keith Earls (Munster/Ireland)
14. Shane Williams (Ospreys/Wales)
13. Riki Flutey (London Wasps/England)
12. Gordon D'Arcy (Leinster/Ireland)
11. (Leinster/Ireland)
10. James Hook (Ospreys/Wales)
9. Mike Blair (Edinburgh/Scotland)
8. (Cardiff Blues/Wales)
7. Joe Worsley (London Wasps/England)
6. Nathan Hines (Perpignan/Scotland)
5. Donncha O'Callaghan (Munster/Ireland) captain
4. Simon Shaw (London Wasps/England)
3. Euan Murray (Northampton/Scotland)
2. Ross Ford (Edinburgh/Scotland)
1. Andrew Sheridan (Sale Sharks/England)