Several divinyl ether and diepoxide monomers bearing an azobenzene moiety were synthesized and used to investigate the photoalignment of a ferroelectric liquid crystal (FLC) with no use of surface orientation layers. Azobenzene polymer networks, obtained by cationic polymerization of the monomers dissolved in the FLC host and exposed to linearly polarized irradiation, were found to be able to induce and stabilize a bulk alignment of FLC. Photoinduced reorientation of the FLC can also be achieved by changing the polarization of irradiation light, but in contrast with the use of chiral azobenzene poly(meth)acrylates,(1) the results suggest a mechanism based on the formation of an anisotropic azobenzene polyether or polyepoxide network for the commanding effect on the FLC alignment.