The solubility of calcium formate (form alpha) in four different binary solvent mixtures (methanol + water, ethanol + water, n-propanol + water, and acetone + water) from 283.15 to 323.15 K was measured by a static equilibrium method under atmospheric pressure. Results indicated that the solubility increased with the increasing temperature and water content in binary mixed solvents. The modified Apelblat equation, the combined nearly ideal binary solvent/Redlich-Kister equation, and the Jouyban-Acree equation were applied for the correlation of experimental solubility, among which the modified Apelblat equation was found to be the best fitting model for the crystallization of calcium formate (form alpha). This experimental data can be a fundamental guide to choose a suitable crystallization process for calcium formate in industry.