In this paper, a study of the effect of Al substitution on the upper critical field, B-c2, in AlxMg1-xB2 samples is presented. We find a straightforward correlation between B-c2 and the sigma-band gap, Delta(sigma), evaluated by point-contact measurements. Up to x=0.2, B-c2 can be well described within a clean limit model and its decrease with x is directly related to the suppression of Delta(sigma).