Low-cost poly (3,4 ethylenedioxythiophene) (PEDOT) films with a high electronic conductivity of 1021 S/cm were successfully deposited via iron oxide-based vapor-phase polymerization and used as a counter electrode (CE) in dye-sensitized solar cells for the first time. Reaching a high efficiency of 8.4%, the CE showed outstanding catalytic activity in iodine/triiodide (I-/I-3(-)) reduction, with a six times lower charge transfer resistance than a standard Pt CE. Combining low cost, easy fabrication, and high electro-catalytic activity, our PEDOT films are a promising replacement for expensive platinum CEs. This efficiency is one of the highest reported among the PEDOT-based DSSC.