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Four organic small-molecule hole transport materials (D41,D42,D43 and D44) of tetraarylpyrrolo[3,2-b]pyrroles were pre-pared.They can be used without doping in the manufacture of the inverted planar perovskite solar cells.Tetraarylpyrrolo[3,2-b]pyrroles are accessible for one-pot synthesis.D42,D43 and D44 possess acceptor-π-donor-π-acceptor structure,on which the aryl bearing substitutes of cyan,fluorine and trifluoromethyl,respectively.Instead,the aryl moiety of D41 is in presence of methyl with a donor-π-donor-π-donor structure.The different substitutes significantly affected their molecular surface charge distribution and thin-film morphology,attributing to the electron-rich properties of fused pyrrole ring.The size of perovskite crystalline growth particles is affected by different molecular structures,and the electron-withdrawing cyan group of D42 is most conducive to the formation of large perovskite grains.The D42 fabricated devices with power conversion efficiency of 17.3％ and retained 55％ of the initial photoelectric conversion efficiency after 22 days in dark condition.The pyrrolo[3,2-b]pyrrole is efficient electron-donating moiety for hole transporting materials to form good substrate in producing perovskite thin film.