AbstractPoly[styrene‐co‐(diethyl vinylbenzylphosphonate)] and poly[methylmethacrylate‐co‐(diethyl vinylbenzylphosphonate)] were prepared and used in modified Horner‐Emmons reactions to synthesize polymers with covalently attached stilbene groups. This versatile new method allowed for the preparation of polymers with either electron‐donor (OCH3, CH3) or electron acceptor (Br, NO2) substituents on the stilbene aromatic ring. The resulting polymers were characterized by 1H NMR, FT‐IR, UV‐visible, DSC, and size exclusion chromatography. Efficient transformation of polymeric phosphonates to the polymeric stilbene derivatives was realized. Size exclusion chromatographic analyses demonstrated that the reaction conditions have no deleterious effect on the molecular weight distribution of the various polymers that were prepared. Photochromic behavior was demonstrated for one of the derivatives. © 1995 John Wiley & Sons, Inc.