Abstract Two novel and simple donor‐π‐bridge‐donor (D‐π‐D) hole‐transporting materials (HTMs) containing two units of the p ‐methoxytriphenylamine (TPA) electron donor group covalently bridged by means of the 3,4‐dimethoxyselenophene spacer through single and triple bonds are reported. The optoelectronic and thermal properties of the new selenium‐containing HTMs have been determined using standard experimental techniques and theoretical density functional theory (DFT) calculations. The selenium‐based HTMs have been incorporated in mesoporous perovskite solar cells (PSCs) in combination with the triple‐cation perovskite [(FAPbI 3 ) 0.87 (MAPbBr 3 ) 0.13 ] 0.92 [CsPbI 3 ] 0.08 . Limited values of power conversion efficiencies, up to 13.4 %, in comparison with the archetype spiro‐OMeTAD (17.8 %), were obtained. The reduced efficiencies showed by the new HTMs are attributed to their poor film‐forming ability, which constrains their photovoltaic performance due to the appearance of structural defects (pinholes).