Conducting polymers directly grown on a supporting substrate through electrochemical methods present improved electrical contact and adherence compared to those deposited from solution. This paper explores different potentiostatic approaches for the electropolymerization of triphenylamine and the prospects of application of the resulting films as inexpensive cathodes for solid-state solar cells. To this end, solid films of the monomer were deposited onto transparent conducting glass and electrochemically cross-linked to different extents. The polymer films were characterized by CV, in situ UV-Vis Spectroscopy, in situ Electrochemical Quartz Crystal Microbalance, and, then, tested as cathodes in an all-solid-state hybrid mesoscopic solar cell based on TiO2 sensitized with CdSe quantum dots. The results indicate that, through the control of the doping state of the p-semiconductor, the Fermi level of the cathode can be tuned to raise the open-circuit voltage of the cells up to values near +0.8 V. (C) 2014 The Electrochemical Society. All rights reserved.