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Recently, the design and fabrication of lead (Pb)-free perovskite or perovskite-like materials have received great interest for the development of perovskite solar cells (PSCs). Manganese (Mn) is a less toxic element, which may be an alternative to Pb. In this work, we explored the role of NH₃(CH₂)₂NH₃MnCl₄ perovskite as a light absorber layer via SCAPS-1D. A Pb-free PSC device (FTO/TiO₂/NH₃(CH₂)₂NH₃MnCl₄/spiro-OMeTAD/Au) was simulated via SCAPS-1D software. The simulated Pb-free PSCs (FTO/TiO₂/NH₃(CH₂)₂NH₃MnCl₄/spiro-OMeTAD/Au) showed decent power conversion efficiency (PCE) of 20.19%. Further, the impact of the thickness of absorber (NH₃(CH₂)₂NH₃MnCl₄), electron transport (TiO₂), and hole-transport (spiro-OMeTAD) layers were also investigated. Subsequently, various electron transport layers (ETLs) were also introduced to investigate the role of ETL. In further studies, an NH₃(CH₂)₂NH₃MnCl₄-based PSC device (FTO/TiO₂/NH₃(CH₂)₂NH₃MnCl₄/spiro-OMeTAD/Au) was also developed (humidity = ~30–40%). The fabricated PSCs displayed an open circuit voltage (Voc) of 510 mV with a PCE of 0.12%.