Crystalline vaterite is the most thermodynamically unstable polymorph of anhydrous calcium carbonate (CaCO3), and various morphologies can be controlled in the presence of organic additives. Constructing vaterite with minimal defects, determining its distinctive properties, and understanding the formation mechanism behind a biomimetic process are the main challenges in this field. In this paper, a unique single-crystal-like vaterite hexagonal bifrustum with two hexagonal and 12 trapezoidal faces has been fabricated through a catanionic surfactant-assisted mineralization approach for the first time. Compared with the polycrystalline vaterite aggregates, these bifrustums clearly present a doublet for Raman v1 symmetric stretching mode, a low depolarizaiton ratio for carbonate molecular symmetry, and a high structural stability. These indicate a dominant position of hexagonal phase in each crystallite and confirm the Raman v1 doublet characteristics of synthetic and biomineral-based vaterites. Our finding may provide evidence to distinguish vaterite with different structures and shed light on a possible formation mechanism of vaterite single crystals.