PPy/GCA thin films were deposited on FTO substrates and used as a CE in DSSCs. The presence of GCA greatly improved the catalytic performance of the PPy CE, resulting in an enhancement of the photocurrent and photovoltaic performance of the DSSCs. According to the characterization by CV, Tafel and EIS, PPy/GCA CE showed good electrocatalytic activity for triiodide reduction, and low charge transfer resistance on the electrolyte/electrode interface, respectively. The PCE obtained for the DSSC with the PPy/GCA electrode was 7.33%, which is approximately 13% higher than that of the PPy CE (6.48%), and comparable to that of the Pt-based cell (7.54%), indicating that the incorporation of GCA is an efficient means of enhancing the photovoltaic performance based on the conductive polymer PPy. The work reported in this paper was far from being optimized, but the above mentioned advantages along with the low cost synthesis, simpler preparation process and scalable materials highlight the potential of the new PPy/GCA CE as a strong candidate in DSSCs.