A series of novel bifunctionalized photochromic monomers were synthesized, focusing on those with polymerizable acrylic/methacrylic groups attached to both ends of an azobenzene core via flexible spacers. The phase behaviour of the monomers was investigated using DSC, polarizing optical microscopy and X‐ray diffraction. The change in UV‐vis absorbance of the monomers under illumination with non‐polarized/polarized UV light was studied for both solutions and thin films; also studied was its relaxation in the dark. On illumination with LPUV light, in‐plane reorientation of the molecules normal to the polarization of the exciting UV light, and aggregation of the molecules in the films, were found.