Self-assembling of amphiphilic copolymers via microemulsion technique provides versatile platform for physical encapsulation of various sensitive functional molecules. In this work, a novel amphiphilic block poly(arylene ether nitriles) (b-PEN) has been firstly synthesized through the step-growth nucleophilic substitution polycondensation of bisphenol A (BPA) modified hydrophobic oligomer and the hydrophilic oligomer containing pendant sulfonate groups. Due to the incompatibility between the two segments, the isotropic b-PEN superparticles were prepared by a facile microemulsion self-assembly technique, which meanwhile allowed encapsulation of the hydrophobic photosensitizer of ZnPc into the polymeric superparticles. Finally, the stable aqueous solution containing b-PEN@ZnPc hybrid superparticles is obtained and demonstrates singlet oxygen generation ability, which ensures desirable photocatalytic degradation of rhodamine B (RhB). Based on the intrinsically chemical resistance, high mechanical strength and facile fabrication of b-PEN superparticles, the present work will open the way for the construction of robust PEN nanostructures, which could act as the template to assemble with various organic or inorganic functional particles to expand its environmental remediation application. (C) 2017 Elsevier B.V. All rights reserved.