A series of anthracene-based dyes were designed and employed in dye-sensitized solar cells in which different 9,10-diaryl-substituted anthracene groups acted as a π-bridge with 2,6-linkage mode. The tert-butylphenyl and hexyloxyphenyl groups in the 9 and 10 positions of the anthracene unit were almost perpendicular to the conjugated plane, which would be beneficial to suppressing the possible π–π stacking and retarding the charge recombination. Their photophysical properties and photovoltaic performance could be tuned by the modification of the substituted groups to the anthracene ring in some degree. Consequently, dye LI-59-based solar cells gave the best performance, with a Jsc (short circuit current) of 13.42 mA cm–2, Voc (open circuit voltage) of 722 mV, and FF (fill factor) of 0.66, corresponding to an overall conversion efficiency of 6.42% without the presence of CDCA.