•Different diarylamino substituents have different electron donating abilities.•The porphyrin meso diarylamino substituent has a significant influence on the overall solar energy conversion efficiency.•Fukui function has been employed to evaluate nucleophilicities and electron-donating abilities of amino nitrogen.A series of novel zinc porphyrins which are featured with a donor–π–acceptor structure have been synthesized for use in the dye-sensitized solar cells. Various diarylamine moiety, such as diphenylamine, iminodibenzyl or iminostilbene, is introduced at porphyrin meso position as an electron donating group. The cell fabricated with the iminodibenzyl-substituted porphyrin sensitizer yields a short circuit photocurrent density of 9.68 mA/cm2, an open-circuit voltage of 740 mV, and a fill factor of 73.48%, corresponding to an overall conversion efficiency (η) up to 5.26%, which is greater than those obtained by diphenylamine- and iminostilbene-substituted porphyrin-sensitized solar cells (η = 4.05% and 2.62%, respectively). The theoretical studies reveal that the iminodibenzyl donor has the strongest electron donating ability among all three diarylamine substituents employed, which is believed to play a significant role in influencing the photovoltaic properties of these sensitizer-based solar cells.