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The performance enhancement of inverted perovskite solar cells applying nickel oxide (NiOx) as the hole transport layer (HTL) has been limited by impurity ions (such as nitrate ions). Herein, we have proposed a strategy to obtain high-quality NiOx nanoparticles via an ionic liquid-assisted synthesis method (NiOx-IL). Experimental and theoretical results illustrate that the cation of the ionic liquid can inhibit the adsorption of impurity ions on nickel hydroxide through a strong hydrogen bond and low adsorption energy, thereby obtaining NiOx-IL HTL with high conductivity and strong hole-extraction ability. Importantly, the removal of impurity ions can effectively suppress the redox reaction between the NiOx film and the perovskite film, thus slowing down the deterioration of device performance. Consequently, the modified inverted device shows a striking efficiency exceeding 22.62 %, and superior stability maintaining 92 % efficiency at a maximum power point tracking under one sun illumination for 1000 h.