Various crystal forms of calcium carbonate were successfully synthesized with CaCl2 and Na2CO3 in 10%(V/V) egg white protein solution system at 20 °C, 40 °C and 60 °C, respectively. The obtained calcium carbonate were characterized by SEM, XRD, FTIR and TG. In addition, the possible mechanism of crystal formation were analyzed. The results indicated that egg white protein could regulate the crystal forms of calcium carbonate and the calcium carbonate, which contained a small amount of egg white protein and consisted of mixed calcite and aragonite, was mainly spherical. With the temperature rosing, the vaterite content gradually increased while the calcite decreased.