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In recent times, research communities are working on device to harvest solar energy at low cost. Copper‐based quaternary chalcogenides are one among the leading materials in the field. Herein, the electrical and optical performance of quantum well embedded Cu 2 - Fe - Sn - normalS 4 (CFTS) solar cell is investigated in detail. Multiple quantum wells (MQWs) with different bandgaps ensure wider photon absorption of solar spectrum. Hence, MQWs made up of CFTSe/CFTS are incorporated with a variation in well size and well numbers. All the electrical parameters and optical parameters such as power conversion efficiency, quantum efficiency, and its dependence on carrier quantization are discussed in detail. More than 80% external quantum efficiency with just 2 QWs shows the efficient carrier generation and collection of the proposed structure. Device with 10 QWs of size 18/10 nm of CFTSe/CFTS can achieve remarkable efficiency of 21% with good trade‐off between J sc and fill factor.

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