Andy Robinson named Al as his skipper after being impressed with the way the Glasgow Warriors lock led Scotland to their first series win in the southern hemisphere in Argentina last summer.
Al resumes his role after missing the Autumn Test series following knee surgery.
Robinson used scrum-halves Rory Lawson and Mike Blair as his captains during the Autumn Series, during which Scotland beat South Africa and Samoa.
But the Glasgow captain's displays since returning from injury have persuaded Robinson to revert to the 29-year-old, who led Scotland to a famous win over Australia in 2009 when Chris Cusiter was injured.
Robinson said: "Al's leadership on and off the field was a key element to our success in Argentina and, since his return from knee surgery, the quality of both his personal displays and the way he has galvanised the Glasgow side, especially over the last month, has been really pleasing.
"I have spoken about the importance of broadening the influence of leaders throughout the side and Rory Lawson, Mike Blair and Chris Cusiter have all led the side well."
Al will lead Scotland out at the Stade de France a week on Saturday.
He told www.scottishrugby.org: "To get the chance to captain Scotland for the opening Six Nations game is huge.
"I was delighted to make the squad, especially after being out for almost six months with my knee after Argentina, and now to be named as captain is a real highlight, particularly with the competition for places."