In this paper, we report on the synthesis, characterization of a new triphenylamine (TPA) derivative (TPAR14) with a "secondary electron transferring" structure as well as its application to dye-sensitized solar cells (DSCs). The introduction of diphenylvinyl to the adjacent phenyl ring of the TPA core could not only increase the extinction coefficient and lambda(max) by the extension of pi-conjugation, but also form three-dimensional obstacle for dye aggregation and triiodide that is in favor of higher open-circuit photovoltage (V-oc). An overall light-to-electricity conversion efficiency of 6.27% is obtained for the DSC with the assynthesized dye under AM 1.5 irradiation (100 mW cm(-2)), which is the highest value among the TPA-rhodanine-3-acetic acid-based DSCs. The long-term stability test of TPAR14 under heat shows its character of high stability. The present work indicates that the as-synthesized TPAR14 is promising in the application of DSCs. (C) 2008 Elsevier B.V. All rights reserved.