Nickel-phthalocyanines (NiPc) with planar aromatic structures are ideal building blocks for organic nanostructures. They can self-assemble into stacks through π–π interaction, exhibit high thermal and chemical stabilities, and possess outstanding electrical and optical properties. Herein, single-crystal NiPc nanorods were synthesized by a facile vapor transfer deposition method. Their nanostructures and compositions were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) in detail. The deposited NiPc nanorods were found to be the β-phase single crystals. Moreover, the NiPc nanorod-based devices were fabricated and exhibited high photocurrent upon white-light illumination. This indicates that the NiPc nanorods can be considered as a candidate material for fabricating photoelectric devices.