In this paper we review our recent studies of the surface characterization of commercially available indium-tin-oxide (ITO) thin films, using photoelectron spectroscopies (XPS and UPS) and electrochemistry of chemisorbed probe molecules such as ferrocene dicarboxylic acid (Fc(COOH)(2)). The modification of these ITO films through chemisorption of carboxylic acid-substituted small molecules, such as Fc(COOH)(2), 3-thiophene acetic acid (3-TAA), and the subsequent modification of these interfaces with electrochemically grown conducting polymer (CP) films is also introduced. We report preliminary results of our studies changes in performance of vacuum deposited organic photovoltaic (PV) cells as a result of these ITO substrate modification steps. The surfaces of as-received ITO films, and those cleaned by various solution and plasma-etching processes, are unavoidably hydrolyzed to In(OH)(3)-like and InOOH-like surface species, which leaves the ITO surface with at most 40-50% of the electronically active sites available for electron transfer reactions. Modification of the ITO surface with electroactive small molecules such as Fc(COOH)(2) and 3-TAA provides for better wettability of organic layers to the polar ITO surface and enhanced electrical contact (lower series resistance, R-S) between the ITO anode, spin-cast or electrodeposited PEDOT:PSS layers and copper phthalocyanine (CuPc) layers in multilayer (CuPc/C-60/BCP) excitonic PV cells. Improvements in PV J/V (current/voltage) responses are noted mainly through increases in short-circuit photocurrent and lowered series resistances (R-S) when electroactive small molecules are chemisorbed to the ITO surface, prior to spin-casting of conducting polymer, PEDOT:PSS, layers. (C) 2003 Elsevier B.V. All rights reserved.