Many times that the story of the Wayne's being murdered is told in the comics, the going-out-to-cinema is either a regular special event for the family (in spite of being really wealthy they wanted to do a "normal" family thing) or is a reward or treat for Bruce, for one reason or another.
The thing is that the Waynes wanted to enjoy that night by themselves, so Alfred wasn't chauffeuring them to start with. Given the time of the event, and the fact that as a butler he is some kind of in house service, he was probably at the Wayne Manor, available but not really working at the time (it seems that Alfred is an avid book reader), but he might have been cleaning the silver as well, for example.
In the story Zero Hour, Batman sort of travels to an alternate timeline where Bruce was killed that night, and his parents survive. When he gets to Wayne Manor Alfred is there, but it seemed he wasn't working, since he wasn't wearing all his "butler outfit", so he could have been resting/relaxing. When doctor Wayne and his wife come with the police and bad news, Martha Wayne requests Alfred to help some drinks to the police officers, and he gets back to work.
In other stories, such as Batman Earth One, which is a retold of the story,
Alfred is actually a friend from the military service of Thomas Wayne. He advises Thomas not to go by themselves to the theater, but Thomas insists, since he wants "a normal life" for Bruce. After the death of his parents Alfred has to assume guardianship of a really enraged Bruce, and he lies to him, telling that he was hired as his butler, as a excuse to be able to stay there and take care of him.
Apart from that, not much has actually ever been discussed in the comics about Alfred whereabouts that night, so I think that assuming that he was at the Manor, on call but not really working might be the safest bet.