The photorefractivity of a non‐conjugated main‐chain polymeric composite, composed of electron‐rich N,N‐di‐toly‐N,N′‐diphenylbiphenyldiamine doped with 2‐{3‐[(E)‐2‐(piperidino)‐1‐ethenyl]‐5,5‐dimethyl‐2‐cyclohexenylidene}‐malononitrile (P‐IP‐DC) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM), is studied using two‐beam coupling and degenerate four‐wave mixing at 633 nm. The N,N′‐di‐toly‐N,N′‐diphenylbiphenyldiamine‐based composite shows a gain coefficient of 215 cm−1 at 80 V μm−1 with s‐polarized beams and a diffraction efficiency of 67% at 30 V μm−1, with a response time of the diffraction efficiency of 344 ms at Tg + 4.6 °C. Comparing the photorefractive grating response time of the 3,3′‐dicarbazole‐containing polymer composite with that of the N,N′‐di‐toly‐N,N′‐diphenylbiphenyldiamine‐based composite shows that the former is more than three times faster.