Six triphenylamine-based dyes were explored for their application in dye-sensitized solar cells (DSSCs). Dyes 1-3 and dyes 4-6 possess cyanoacrylic acid (C-acceptor) and rhodanine-3-acetic acid (R-acceptor), respectively. Stilbene (in dyes 2 and 5) and bis(styryl)benzene (in dyes 3 and 6) were used as pi-spacers. There is no pi-spacer in the dye 1 and 4. To elucidate the role of pi-spacers, optical, electrochemical, and photovoltaic properties of the dyes were studied. Among C-acceptor dyes, dye 2 exhibits the highest light-to-electricity conversion efficiency of 4.45%, followed by dye 3 (4.16%). Similarly, among R-acceptor dyes, dye 5 is the best. These results indicate that stilbene is a better pi-spacer over bis(styryl) benzene. Although bis(styryl)benzene could extend the light absorption range (in dye adsorbed TiO2 film), its tendency to promote intermolecular pi-pi stacking is possibly the reason for its poor performance in DSSCs. Furthermore, the conjugation break in the R-acceptor moiety attached to the TiO2 surface limits the electron injection of R-acceptor dyes poorer than C-acceptor dyes. Density functional theory calculations were performed for the dye-(TiO2)(8) cluster, assuming a bidentate chelation of a carboxylic acid group with Ti4+ of TiO2 anatase. The natural bond orbital (NBO) analysis indicated relatively more electron-accepting ability of cyanoacrylic acid over rhodanine-3-acetic acid. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.