Three hole-transporting materials (HTMs) based on the phenothiazine core containing 4,4-dimethyltriphenylamine (Z28), N-ethylcarbazole (Z29), and 4,4-dimethoxytriphenylamine (Z30) as the peripheral groups connected by double bonds were designed and synthesized. The HTMs were tested in mixed cation/anion perovskite solar cells (PSCs) of the composition [(FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 ]. A power conversion efficiency (PCE) of 19.17% under 100 Mw cm −2 standard AM 1.5G solar illumination was obtained using Z30. Importantly, the devices based on Z30 show better stability compared to those using Z28 and Z29 when aged under ambient air of 40% relative humidity in the dark for 1008 h and under continuous sunlight soaking without encapsulation for 600 h. These results indicate that the 4,4-dimethoxytriphenylamine is a promising peripheral group in combination with the phenothiazine core, providing an alternative to develop small molecular HTMs for efficient and stable PSCs.