The exploration of alternative low-cost molecular hole-transporting materials (HTMs) for both highly efficient and stable perovskite solar cells (PSCs) is a relatively new research area. Two novel HTMs using the thiophene core were designed and synthesized (Z25 and Z26). The perovskite solar cells based on Z26 exhibited a remarkable overall power conversion efficiency (PCE) of 20.1%, which is comparable to 20.6% obtained with spiroOMeTAD. Importantly, the devices based-on Z26 show better stability compared to devices based on Z25 and spiroOMeTAD when aged under ambient air of 30% or 85% relative humidity in the dark and under continuous full sun illumination at maximum power point tracking respectively. The presented results demonstrate a simple strategy by introducing double bonds to design hole-transporting materials for highly efficient and stable perovskite solar cells with low cost, which is important for commercial application.