A series of facile small-molecular D-π-D HTMs with dibenzofuran or dibenzothiophene as π-bridge, and the triarylamine groups as peripheral arms was designed and prepared. The impact of the varied substitution position of triarylamine groups on the π-bridge and heteroatomic effect on the molecular and device properties are extensively studied. All the molecules exhibit suitable energy alignment of the HOMO with the valence band of perovskite. 3,7-molecules showed red-shift spectra compared to that of 4,6 and 2,8-counterparts, indicating the better conjugation. Due to the better hole extraction and conductivity of 3,7-molecules because of enhanced conjugation, which exhibits relatively best power conversion efficiency. 4,6-substituents exhibit inferior device performance due to the broken conjugation of 4,6-position and bad filmforming ability. Moreover, the O-based HTMs exhibit relatively better device performance when the terminal groups are located on 3,7-position due to enhanced hole extraction ability. However, the heteroatom effect of 4,6-substituent is contrary with 3,7-counterpart due to the opposite conductivity change trend.