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The density of glycine, L-alanine, and L-serine in formamide− water mixtures was measured at 298.15 K and used to calculate the apparent molar volume V ϕ and limiting partial molar volume V ϕ °of the amino acids. Transfer partial molar volume Δ tr V ϕ °from water to formamide−water mixtures and the volumetric interaction coefficients were also obtained to interpret the solute−solvent interaction. Values of Δ tr V ϕ °of the three amino acids were all positive and increased with increasing formamide concentration in the mixtures, in the order of L-alanine < glycine < L-serine, which was consistent with the cosphere overlap model. The interaction of formamide molecules decreased its structural-breaking effect and consequent interaction with amino acids, leading to negative triplet interaction coefficients.