The effect of rapid oxidation temperature on the sputtered nickel (Ni) films to act as a hole transport layer (HTL) for perovskite solar cell (PSCs) was investigated. A nano-sputtered Ni film with a thickness about 100 nm was oxidized at a range of different oxidation temperatures between 350 and 650 °C to work as HTL in an inverted p–i–n configuration. DC Hall measurement in van der Pauw configuration and photoluminescence spectroscopy were used to measure the charge’s mobility and extraction of nickel oxide (NiO) films. The behaviour of the carrier concentration measurements of NiO layers at different oxidation temperatures showed that the Ni layer oxidized at 450 °C had the highest carrier concentration among the other samples. The performance measurements of the fabricated PSCs showed that the nickel oxide hole-transporting layer which has been oxidized at the optimum oxidation temperature of 450 °C has the highest power conversion efficiency (PCE) of 12.05%. Moreover, the characteristic parameters of the optimum cell such as the open-circuit voltage (VOC), short-circuit current density (JSC) and fill factor (FF) were 0.92 V, 19.80 mA/cm2 and 0.331, respectively.