The fundamental optical storage mechanism of the laser light addressable azobenzene moiety is briefly introduced.A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularly spaced side chains. Thin films of these materials are particularly well suited for holographic storage. Notable figures of merits of liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacity expressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50% or greater,and erasability. The implications of the main chain nature for polyester morphology and for the permanency of the induced anisotropy are discussed. The design and methods of preparation of other significantly different polymer scaffolds supporting cyanoazobenzene are elaborated. Oligopeptides always result in amorphous materials, whereas copolymethacrylates and dendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these scaffolds affords materials that result in permanent anisotropy when exposed to interfering laser light.