Selective, stable, molecularly imprinted polymers having intrinsic photoresponsive properties were synthesized for the purpose of photoregulated binding of a predetermined ligand. Highly crosslinked, free-standing polymer membranes were synthesized from an optimized mixture of two cross-linkers-ethylene glycol dimethacrylate and tetraethylene glycol diacrylate. For synthesizing molecularly imprinted polymers, p-phenylazoacrylanilide (PhAAAn) was used as a new photoresponsive functional monomer. A study of the kinetics of photoisomerization of PhAAAn within the polymer membranes before and after treatment with various media showed the excellent functional stability of the membranes. Polymer membranes synthesized in the presence of the template dansylamide possess selective sites for recognizing dansylamide, and the affinity of these sites can be reversibly changed by illumination with ultraviolet or visible light.