In this study, for the first time, n-i-p PSCs were fabricated using dopant-free 2,7-dioctyl1benzothieno3,2- b 1benzothiophene (C8-BTBT) as the solution-processed hole transporting layer (HTL). The power conversion efficiency (PCE) of the optimized device with the C8-BTBT film that favored edge-on molecular alignment was 22.45% with negligible hysteresis. A thinner dopant-free C8-BTBT HTL effectively protected the perovskite layer from moisture resulting in better shelf-life stability for un-encapsulated PSCs, which maintained >80% of its initial PCE (after a period of 120 days) at a relative humidity level of 40-45%. In addition, the C8-BTBT-based PSCs kept their high performance with no obvious PCE loss at 60 °C for 20 days in the ambient atmosphere and retained 82% of their initial PCE at 85 °C for 10 days. Overall, our findings revealed that a thin solution-processed C8-BTBT HTL plays a critical role not only in hole extraction and transport but also in greatly improving the ambient and thermal stability of n-i-p PSCs. Herein, we have demonstrated n-i-p PSCs with an efficiency of 22.45% and high thermal stability using dopant-free 2,7-dioctyl1benzothieno3,2- b 1benzothiophene (C8-BTBT) as the solution-processed hole transporting layer (HTL).