We report here on the synthesis and photophysical/electrochemical properties of three functional triarylamine organic dyes (MXD5−7) as well as their application in dye-sensitized nanocrystalline TiO2 solar cells (DSSCs). For the designed dyes, the nonplanar structures of bis-hexapropyltruxeneamino take the role of electron donor. The introduction of bis-hexapropyltruxeneamino units brought about superior performance over the simple triphenylamine dye, in terms of light-capturing abilities and suppressing dye aggregation. Among three dyes, the DSSCs based on the dye MXD7 showed the best photovoltaic performance: a short-circuit photocurrent density (JSC) of 11.8 mA cm−2, an open-circuit photovoltage (VOC) of 772 mV, and a fill factor (ff) of 0.68, corresponding to an overall conversion efficiency of 6.18% under 100 mW cm−2 irradiation. These dyes exhibited high VOC values, possible origin for which was investigated regarding the TiO2 surface blocking, conduction band movement, and electrolyte-dye interaction.