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Metal halide perovskites have raised huge excitement in the field of emerging photovoltaic technologies. The possibility of fabricating perovskite solar cells (PSCs) on lightweight, flexible substrates, with facile processing methods, provides very attractive commercial possibilities. Nevertheless, efficiency values for flexible devices reported in the literature typically fall short in comparison to rigid, glass‐based architectures. Here, a solution‐processable fullerene derivative, [6,6]‐phenyl‐C61 butyric acid n‐hexyl ester (PCBC6), is reported as a highly efficient alternative to the commonly used n‐type materials in perovskite solar cells. The cells with the PCBC6 layer deliver a power conversion efficiency of 18.4%, fabricated on a polymer foil, with an active area of 1 cm2. Compared to the phenyl‐C61‐butyric acid methyl ester benchmark, significantly enhanced photovoltaic performance is obtained, which is primarily attributed to the improved layer morphology. It results in a better charge extraction and reduced nonradiative recombination at the perovskite/electron transporting material interface. Solution‐processed PCBC6 films are uniform, smooth and displayed conformal capping of perovskite layer. Additionally, a scalable processing of PCBC6 layers is demonstrated with an ink‐jet printing technique, producing flexible PSCs with efficiencies exceeding 17%, which highlights the prospects of using this material in an industrial process.