The novel photoresponsive molecularly imprinted polymers (P-MIPs) based on mesoporous carriers were developed for selective recognition and intelligent separation of bisphenol A from the complex samples. P-MIPs were prepared using an azobenzene-containing monomer as the photosensitive monomer by a facile free radical polymerization, combining the stimuli responsive mechanism and imprinting technology. The physical property and structure of newly synthesized materials have been characterized, and their photoisomerization properties were studied. P-MIPs displayed a superior photoresponsive property. Interestingly enough, the template molecules can be easily bound in the recognition sites and released back into the solution under the alternating irradiation. Binding properties of P-MIPs were also further evaluated by batch adsorption experiments. They possessed specific recognition sites and higher affinity for BPA, and the maximal adsorption capacity was 27.06 mol g(-1). Subsequently, the materials were also successfully applied to photocontrolled separation of BPA in real water sample with good recovery, indicating great applicability for selective removal specific analytes from complex environment. The present work mainly provided the deep analysis and useful insights concerning the feasibility of using stimuli responsive imprinted materials in intelligent separation system, which shows tremendous potential to establish a sustainable environment. (C) 2016 Elsevier B.V. All rights reserved.