Electron microscopy observations of α–ZrP whiskers with the NaCl structure, grown by chemical vapor deposition at 1300 °C, showed that there exists a hexagonal structure region (a = 0.369 nm and c = 1.248 nm) near the surface of the whiskers. High-resolution lattice image observations revealed that the method of stacking the eight-layered hexagonal structure is different from the reported hexagonal β–ZrP. In addition to the eight-layered structure, 12-layered and 16-layered structures were also observed, indicating a variety of ZrP polymorphisms.