The cornerstones of emerging high-performance organic photovoltaic devices are bulk heterojunctions, which usually contain both structure disorders and bicontinuous interpenetrating grain boundaries with interfacial defects. This feature complicates fundamental understanding of their working mechanism. Highly-ordered crystalline organic p-n heterojunctions with well-defined interface and tailored layer thickness, are highly desirable to understand the nature of organic heterojunctions. However, direct growth of such a crystalline organic p-n heterojunction remains a huge challenge. In this work, we report a design rationale to fabricate monolayer molecular crystals based p-n heterojunctions. In an organic field-effect transistor configuration, we achieved a well-balanced ambipolar charge transport, comparable to single component monolayer molecular crystals devices, demonstrating the high-quality interface in the heterojunctions. In an organic solar cell device based on the p-n junction, we show the device exhibits gate-tunable open-circuit voltage up to 1.04 V, a record-high value in organic single crystalline photovoltaics.