The invention discloses calcium-based titanium dioxide and a preparation process thereof. The calcium-based titanium dioxide is prepared from an outer membrane formed by coating a core substrate made of a 4,000-6,000-mesh superfine calcium carbonate inorganic powder material with titanium dioxide having the meshes of 10,000 or above. According to the preparation process, a uniformly mixed aqueous solution is prepared from superfine calcium carbonate, a uniformly mixed aqueous solution is prepared from titanium dioxide, a uniformly mixed aqueous solution is prepared from a dispersing agent and a coating agent, accordingly, the agglomeration phenomenon is effectively avoided, superfine calcium carbonate effectively keeps in a dispersed state, a PUC control system is used for controlling time, speeds, temperature and electric charge of a three-stage cascade high-speed mill as well as and mechanical chemical reactions, inorganic coating is performed according to the principles of kinetics and thermodynamics, and the outer membrane is uniform and compact in coating and firm in combination. Through drying, curing, homogenized powder and homogenization, modification and membrane repairing, the membrane is smoother, and the whiteness, the oil absorption value and the covering power of a product are effectively improved. Detection proves that the whiteness reaches 97%-99%, the oil absorption value is 29-35 g/100 g, the covering power is higher than 35.4 g/m<2>, and the product indexes all reach or exceed the national standard.