Perovskite solar cells (PSCs) have experienced an outstanding advance in power conversion efficiency (PCE) by employing new electron transporting layers (ETLs), interfaces engineering, optimizing perovskite morphology and improving charge collection efficiency. In this work, we study the role of a new ultrathin interface layer of titanium nitride (TiN) conformally deposited on mesoporous TiO2 (mp-TiO2) scaffold using atomic layer deposition (ALD) method. Our characterization results revealed that the presence of TiN at the ETL/perovskite interface improves the charge collection as well as reduces the interface recombination. We find that the morphology (grain size) and optical properties of the perovskite film deposited on optimized mp-TiO2/TiN ETL are improved drastically leading to devices with a maximum PCE of 19.38% and a high open-circuit voltage (Voc) of 1.148 V with negligible hysteresis and improved environmental (~40% RH) and thermal (80oC) stability.