We investigated the effect generally treated in the literature as inverse relaxation, which is related to an increase in the birefringence of azopolymer films after the inscription laser is turned off. The results demonstrate that films prepared with the casting method on anisotropic substrates induce a preferential organization of the polymeric chains. Inverse relaxation is evidenced only when the photo-alignment of the azo groups is induced parallel to the orientation of the polymeric chains. Thus, it is possible to enhance the optical storage in these systems with appropriate alignment methods. (C) 2013 Elsevier B. V. All rights reserved.