A novel HTM based on silver thiocyanate (AgSCN) was designed to be useable in p-i-n perovskite solar cells (PSCs). With mass yield, the AgSCN was synthesized in the lab and elucidated by XRD, XPS, Raman spectroscopy, UPS, and TGA. The production of thin, highly conformal AgSCN films that allow for quick carrier extraction and the collection was made possible by a fast solvent removal approach. Photoluminescence experiments have shown that adding AgSCN has improved the ability to transfer charges between HTL and perovskite layer compared to PEDOT:PSS at the interface. Crystallographic discrepancies in the polycrystalline perovskite film are discovered upon further examination of the film's microstructure and morphology, pointing to the development of templated perovskite on the surface of AgSCN. In comparison to devices due to the well-known PEDOT:PSS, the open circuit voltage (VOC) is increased by AgSCN with its high work function by 0.1–1.14 V (1.04 V for PEDOT:PSS). With a power conversion efficiency (PCE) of 16.66%, a high-performance PSCs are effectively generated using CH3NH3PbI3perovskite compared to 15.11% for controlled PEDOT:PSS devices.The solution-processed inorganic HTL was demonstrated employing straightforward in order to build durable and effective flexible p-i-n PSCs modules or their use as a front cell in hybrid tandem solar cells.