In our present study, polypyrrole-1 (PPy1), polypyrrole-2 (PPy2), and polypyrrole-2/multi wall carbon nanotube composite film (PPy2/MWCNT) were proposed as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs) to replace the precious Pt CE. These films were fabricated on fluorine-doped tin oxide substrates by using a facile electrochemical polymerization route, and served as CEs in DSSCs. It is shown that the introduction of anionic surfactant, sodium dodecyl sulfate (SDS), enhanced the catalytic activity, thus leading to an improvement in the performance of PPy2. Further, introduction of MWCNT resulted in increase in conversion efficiency of DSSCs with PPy2/MWCNT composite film. The Tafel and electrochemical impedance analysis revealed that the PPy2 and PPy2/MWCNT CEs prepared with anionic surfactant possessed more catalytic activity and lower charge transfer resistance in comparison with PPy1 -based CE. This resulted in a better conversion efficiency of 5.88% for PPy2/MWCNT-based DSSC under 1 sun condition, reaching 86% of the DSSC based on reference Pt counter electrode (6.86%). These results indicate that the composite film with high catalytic properties for I3- reduction can potentially be used as the CE in a high-performance DSSC.