Hollow calcium carbonate (CaCO3) particles were synthesized by bubbling CO2 in the solution of calcium chloride (CaCl2) with the presence of ammonia at room temperature. Hollow calcium carbonate is a potential component to be used as pharmaceuticals, agrochemicals, and catalysis. This paper investigated the effect of additive on the hollow structure. In this study was used vanadate ion as additive agent. Physical characteristics of precipitate were evaluated using scanning electron microscopy (SEM) and X-ray diffraction (XRD).