Several butterfly-shaped materials composed of dibenzo[b,d]thiophene (DBT) and dibenzo-dithiophene (DBT5) cores were designed as hole transporting materials (HTMs) and their properties were studied by density functional theory (DFT) computations for usage in mesoscopic n-i-p perovskite solar cells (PSCs). To choose suitable HTMs, it was displayed that both of lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energies of molecules were located higher than those of CH3NH3PbI3 (MAPbI3) perovskite as they were able to transfer holes from the MAPbI3 toward Ag cathode. Negative solvation energy (ΔEsolvation) values for all HTMs (within the range of − 5.185 to − 18.140 kcal/mol) revealed their high solubility and stability within CH2Cl2 solvent. The DBT5-COMe demonstrated the lowest values of band gap (Eg = 3.544) and hardness (η = 1.772 eV) (the greatest chemical activity) and DBT5-CF3 displayed the biggest η = 1.953 eV (maximum stability) that were predominantly valuable for effective HTMs. All HTMs presented appropriately high LHEs from 0.8793 to 0.9406. In addition, the DBT5 and DBT5-SH depicted the lowest exciton binding energy (Eb) values of 0.881 and 0.880 eV which confirmed they could produce satisfactory results for the PSCs assembled using these materials. The DBT5-SH and DBT5-H had maximum hole mobility (μh) values of 6.031 × 10–2 and 1.140 × 10–2 which were greater than those measured for the reference DBT5 molecule (μh = 3.984 × 10–4 cm2/V/s) and about 10 and 100 times superior to the calculated and experimental μh values for well-known Spiro-OMeTAD. The DBT5-COOH illustrated the biggest open circuit voltage (VOC), fill factor (FF) and power conversion efficiency (PCE) values of 1.166 eV, 0.896 and 23.707%, respectively, establishing it could be as the best HTM candidate for high performance PSCs.