In the present work, densities (ρ) of glycine, l-alanine, aminobutyric acid, l-valine, and l-leucine in an aqueous solution of calcium acetate (0.2005; 0.5998; 0.9000; 1.1978; and 1.5991) mol kg–1 have been measured at T = 293.15–308.15 K and pressure P = 0.1 MPa. The infinite dilution apparent molar volumes (Vφ0) and standard volumes of transfer (ΔtrVφ0) vary linearly with those of carbon atoms in the alkyl chain of the amino acids. The contributions of the nonpolar groups to the value of Vφ0 increase with the size of the alkyl chain of amino acids and decrease with the concentration increase of calcium acetate. The group-contribution of charged end groups (NH3+, COO–) is larger than that corresponding to alkyl chains. The standard transfer volumes (ΔtrVφ0) for all amino acids are positive and increase with the calcium acetate concentrations and decrease with temperature, except for l-valine and l-leucine. Volumetric interaction coefficients of amino acids have been determined using the McMillan–Mayer equation. Calcium acetate shows a strong dehydration effect on amino acids over the entire concentration range. All results show a preferential solvation phenomenon in the mixture due to electrostatic interactions at the first layer solvation between the charged groups of amino acids and the inorganic salt.