The invention discloses a method for preparing double-stimulation responsive surface through secondary photopolymerization, relating to the field of grafting and modification of various base material surfaces. The method comprises the following steps: I, grafting pH responsive compound onto the surface by adopting a cracking type photoinitiator, wherein the pH responsive compound grafted onto the surface can be used as a hydrogen donor and a co-initiator of the next step reaction; and II, performing photopolymerization reaction on the basis by adopting a hydrogen abstracting type initiator, and grafting the double bond-modified photoresponse compound. The method not only has the advantage that the photopolymerization is efficient, energy-saving, economical, environment-friendly, and the like, but also the compound is difficult to drop after being grafted onto the surface through a covalent bond manner. The prepared intelligent surface has good photoresponsiveness, pH responsiveness, and the swelling property and wettability of the surface polymer can be reversibly controlled. The surface has potential application on the aspects of surface molecule switches, surface controlled release and ion adsorption due to good controllable wettability and mechanical effect.