In this paper, we develop high performance poly(3,4-ethylenedioxythiophene) (PEDOT) counter electrodes (CEs) by a vapor deposition method, which gives 6.09% in conversion efficiency for the dye-sensitized solar cell (DSSC) with a thin PEDOT film CE (16 nm in thickness). To increase the quantity of PEDOT deposited on the CEs, we insert an antimony tin oxide (ATO) porous conductive supporting layer to increase the internal deposition area. The conversion efficiency of the DSSC with this PEDOT/ATO composite CE is enhanced to 7.47%.