Here, we report on three new triphenylamine-based enamines synthesized by condensation of an appropriate primary amine with 2,2-diphenylacetaldehyde and characterized by experimental techniques and density functional theory (DFT) computations. Experimental results allow highlighting attractive properties including solid-state ionization potential in the range of 5.33–5.69 eV in solid-state and hole mobilities exceeding 10 –3 cm 2 /V·s, which are higher than those in spiro-OMeTAD at the same electric fields. DFT-based analysis points to the presence of several conformers close in energy at room temperature. The newly synthesized hole-transporting materials (HTMs) were used in perovskite solar cells and exhibited performances comparable to that of spiro-OMeTAD. The device containing one newly synthesized hole-transporting enamine was characterized by a power conversion efficiency of 18.4%. Our analysis indicates that the perovskite–HTM interface dominates the properties of perovskite solar cells. PL measurements indicate smaller efficiency for perovskite-to-new HTM hole transfer as compared to spiro-OMeTAD. Nevertheless, the comparable power conversion efficiencies and simple synthesis of the new compounds make them attractive candidates for utilization in perovskite solar cells.