Excellent hole transporting materials (HTMs) are beneficial to promote the performance of perovskite solar cells (PSCs). Herein, starting from the modulation of the π-conjugated groups of carbazole-diphenylamine derivatives, HTMs CY1 and CY2 were designed and investigated using density functional theory and Marcus theory. Theoretical simulations show that CY1 and CY2 exhibit appropriate HOMO/LUMO energy levels, small recombination energy, good optical properties and molecular stability. Compared with CY1, CY2 with a larger π-conjugated group on its side chain can yield a higher hole mobility and better charge separation. The experimental results confirm that CY2 in PSCs exhibits superior properties such as good hole transporting ability, good film morphology, and efficient charge extraction and dissociation at perovskite/HTM inerfaces. Therefore, a PSC device with CY2 yields a higher efficiency than those of CY1- and Spiro-OMeTAD-based devices. Hence, the results demonstrate that the strategy of the extended π-π conjugation on a side chain is a practicable approach to design potential HTMs for application in PSCs.