This work highlights the utilization of a novel hole-transporting material (HTM) derived from benzothiadiazole: 4-(3,5-bis(trifluoromethyl) phenyl)-7-(5'-hexyl-[2,2'-bithiophen]-5-yl) benzo[c][1,2,5] thiadiazole (CF-BTz-ThR) and aligned TiO2 nano-bundles (TiO2 NBs) as the electron transporting layer (ETL) for perovskite solar cells (PSCs). The aligned TiO2 NBs were grown on titanium (Ti)-coated FTO substrates using a facile hydrothermal method. The newly designed CF-BTz-ThR molecule with suitable highest occupied molecular orbital (HOMO) favored the effective hole injection from perovskite deposited aligned TiO2 NBs thin film. The PSCs demonstrated a power conversion efficiency (PCE) of similar to 15.4% with a short circuit current density (J(SC)) of similar to 22.42 mA cm(-2) and an open circuit voltage (V-OC) of similar to 1.02 V. The efficiency data show the importance of proper molecular engineering whilst highlighting the advantages of dopant-free HTMs in PSCs.