For the purpose of replacing the precious Pt counter electrode in dye-sensitized solar cells (DSSCs) with higher energy conversion efficiency, multi-wall carbon nanotube (MWCNT)/polypyrrole (PPy) double layers film counter electrode (CE) was fabricated by electrophoresis and cyclic voltammetry (CV) layer by layer. Atom force microscopy (AFM), scanning electron microscopy (SEM) and transmission electron microscope (TEM) demonstrated the morphologies of the composite electrode and Raman spectroscopy verified the PPy had come into being. The overall energy conversion efficiency of the DSSC employing the MWCNT/PPy CE reached 3.78%. Compared with a reference DSSC using single MWCNT film CE with efficiency of 2.68%, the energy conversion efficiency was increased by 41.04%. The result of impedance showed that the charge transfer resistance R-ct of the MWCNT/PPy CE had the lowest value compared to that of MWCNT or PPy electrode. These results indicate that the composite film with high conductivity, high active surface area, and good catalytic properties for 13 reduction can potentially be used as the CE in a high-performance DSSC. (C) 2012 Elsevier Ltd. All rights reserved.