Vapor-liquid-liquid equilibrium data for the binary systems 2-methyl-1,3-dioxolane + water and 2,4-dimethyl-1,3-dioxolane + water were collected by using a modified Othmer still vessel at 1 atm of pressure. The UNIQUAC equation of state was fitted to the experimental T-x-x-y data to generate the coefficients of the binary interaction parameters for each system. Vapor pressures for pure 2,4-dimethyl-1,3-dioxolane and 2-methyl-1,3-dioxolane were also measured and used to calculate the constants in Antoine's equation and pure component parameters for each dioxolane. The enthalpy of vaporization calculated from vapor pressure data via the Clausius-Clapeyron equation was in good agreement with the literature value.