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A novel Epitaxial Cadmium Selenide (CdSe) on Lead Selenide (PbSe) type-II heterojunction photovoltaic detector has been demonstrated by Molecular Beam Epitaxy (MBE) growth of n-type CdSe on p-type PbSe single crystalline film. The use of Reflection High-Energy Electron Diffraction (RHEED) during the nucleation and growth of CdSe indicates high-quality single-phase cubic CdSe. This is a first-time demonstration of single crystalline and single phase CdSe growth on single crystalline PbSe, to the best of our knowledge. The current–voltage characteristic indicates a p–n junction diode with a rectifying factor over 50 at room temperature. The detector structure is characterized by radiometric measurement. A 30 μm × 30 μm pixel achieved a peak responsivity of 0.06 A/W and a specific detectivity (D*) of 6.5 × 108 Jones under a zero bias photovoltaic operation. With decreasing temperature, the optical signal increased by almost an order of magnitude as it approached 230 K (with thermoelectric cooling) while maintaining a similar level of noise, achieving a responsivity of 0.441 A/W and a D* of 4.4 × 109 Jones at 230 K.