Numerous efficient extraction methods have been developed for material recovery. However, most of these methods lack selectivity. Recently, we reported electromembrane extraction (EME) as a green, efficient and selective technology for simultaneous extraction and purification of trace targets for sample preparation purpose. Accordingly, EME could be a promising technique on resource conservation, for example, selective recovery of templates with high purity in molecular imprinting. In this work, we first investigated the potential of EME with different configurations for selective recovery of targets at high level (≥ 1000 μg mL⁻¹). A semi-dynamic EME system was applied for EME of a basic template (propranolol) from molecularly imprinted samples prepared by precipitation polymerization and bulk polymerization, and the recoveries were 61% and 55%, respectively. The selectivity of EME for template recovery from real samples was confirmed by UV–vis, HPLC-UV and MS measurements. Moreover, the universality of EME for template recovery was verified by efficient extraction of an acidic template (probenecid). Definitely, EME could be used to solve the historic issue of template recovery in molecular imprinting, and shows great potential for selective extraction of ionizable compounds from complex samples in a single step.