Pursuit of multi-interfacial counter electrodes (CEs) for enhanced triiodide (I-3) reduction reaction has been a persistent objective for dye-sensitized solar cells (DSSCs). Here we report the synthesis of multilayer CEs consisting of positively charged polyaniline-graphene (PANi-G) complex and negatively charged platinum (Pt) nanoparticles. The (PANi-G/Pt)(n) (n represents the bilayer number) multilayer displays multi-interfaces for I-3 reduction and charge transfer. Moreover, the complexation between PANi and G can markedly accelerate the electron migration from G to PANi. The DSSC with (PANi-10wt parts per thousand G/Pt)(9) electrode yields an impressive power conversion efficiency of 7.45% under simulated air mass 1.5 global sunlight. The promising efficiency along with cost-effectiveness and scalable materials demonstrates the multi-interfacial CEs to be good candidates for robust DSSCs. (C) 2015 Elsevier Ltd. All rights reserved.