Hierarchical tree-shaped nanostructures, nanobelts, and nanowires of Zn 3P 2 were synthesized in a thermal assisted laser ablation process. All nanostructures are tetragonal phased Zn 3P 2 with excellent crystallinity and are free from an oxidization layer according to electron microscopy and X-ray diffraction analyses. Optical measurement revealed a strong absorption from the ultraviolet to near-infrared regions. Optoelectronic devices fabricated using individual nanowires demonstrate a high sensitivity and rapid response to impinging light. A crossed heterojunction of an n-type ZnO nanowire and a p-type Zn 3P 2 nanowire has been characterized, and it offers a great potential for a high efficient spatial resolved photon detector.