We report for the first time the synthesis of nonplanar epitaxial tripod nanocrystals of II–VI compounds (ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, and CdTe) on muscovite mica substrate. With CdS as a case study, we conclude via Raman spectroscopy and electron microscopy studies that the tripods, which are found to be polytypic, followed a seeded growth mechanism. The epitaxy, manifested by the in-plane alignment of the legs of the tripods within a substrate, is attributed to the van der Waals interaction between the tripod bases and the mica surface, instead of to the covalent chemical bond which would require lattice matching between the epilayer and the substrate. The results demonstrated herein could have widespread immediate implications, including the potential of van der Waals epitaxy to be applicable in producing ordered arrays of more complex nanoarchitectures from various classes of compounds toward a broad range of technological applications.