Azobenzene monomeric precursors bearing piperazine as donor moiety with different withdrawing groups and derived sidechain polymethacrylates have been prepared and characterized. Monomers having terminal cyano or nitro groups, and the corresponding polymers, exhibited smectic A phases. Linear and nonlinearopticalproperties of every monomer and thin films of the cyano polymer (pol‐PZ‐CN) have been