A polystyrene based visible light responsive polymer bearing donor–acceptor Stenhouse adduct (DASA) pendants is designed and synthesized. Styrene‐vinylbenzyl chloride copolymer (PS‐co‐PCMS) is prepared by free radical polymerization. Then amino‐functionalized PS‐co‐PCMS is obtained by the nucleophilic substitution reaction between the chloromethyl unit and n‐butylamine. Finally, the prepared secondary amines of the polymer are reacted with 5‐(furan‐2‐ylmethylene)‐2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione to fully change them into DASA pendants. The final DASA‐containing polymer shows a tunable photoswitching property upon irradiation with visible light. A photoinduced contact angle change of water on the spin‐coated film of DASA polymer is observed. The DASA polymer film shows excellent photolithographic performance, with well‐defined patterns being efficiently photofabricated using a suitable mask.