Continuing progress in the field of organic polymer photovoltaic (PV) devices requires the development of new materials with better charge-tran sport efficiency. To improve this parameter, we have investigated surface-attached bilayer polymer PV thin films prepared starting from a covalently attached monolayer of an electroactive initiator using sequential electropolymerization of dithiophene and its derivatives. These systems were found to show significantly C increased photocurrent generation quantum yields as compared to systems made through conventional approaches. In addition, the described PV thin films possess remarkable mechanical, air, and photostability. These properties likely arise from the more uniform and better ordered bulk layer morphologies as well as tighter covalently bonded contacts at the interfacial junctions. contributing to improved charge transport. While more studies on the fundamental reasons behind the discovered phenomenon are currently underway, this information can be readily applied to build more efficient organic polymer photovoltaics.