In this study, vibrational (IR and Raman) imaging of two naked and dye-coated TiO2 films (one built from a commercial paste "Dyesol" and one built from an in-house aqueous synthesized anatase variety "Aqueous") is investigated in the high wavenumber region (3000-4000 cm(-1)). Raman and IR imaging showed the distribution of surface Ti-OH/Ti-OH2 groups in Aqueous TiO2 to be qualitatively richer than in Dyesol TiO2. After dye adsorption, the Ti-OH/Ti-OH2 surface group intensity was observed to decrease but still to remain, which provides further supporting evidence that not all surface groups are consumed upon the binding of the dye on the TiO2 surface. The reduced surface group intensity upon adsorption is attributed to regions where bidentate bridging bonding occurs while the remaining Ti-OH/Ti-OH2 groups are proposed to be involved in electrostatic/H-bonding interaction with neighboring carboxylic groups as reported in our previous studies. However, photocurrent-voltage measurements of DSSCs prepared with the two different TiO2 varieties did not produce improved conversion efficiency (g) for Aqueous (4.00 vs. 5.33%). Based on electrochemical impedance spectroscopy analysis of the two different DSSCs, the lack of improvement for the Aqueous TiO2 was traced to extra charge transfer resistance in the photoanode film probably arising from particle aggregation and inefficient electrolyte diffusion (small pore size). (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3582323] All rights reserved.