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We realized photovoltaic operation in large-scale MoS₂ monolayers by the formation of a type-II heterojunction with p-Si. The MoS₂ monolayer introduces a built-in electric field near the interface between MoS₂ and p-Si to help photogenerated carrier separation. Such a heterojunction photovoltaic device achieves a power conversion efficiency of 5.23%, which is the highest efficiency among all monolayer transition-metal dichalcogenide-based solar cells. The demonstrated results of monolayer MoS₂/Si-based solar cells hold the promise for integration of 2D materials with commercially available Si-based electronics in highly efficient devices.