The current study presents the viscosity and density (both experimentally determined and modeled) of five binary mixtures composed of 1,3-dioxolane and 1-alkanol compounds, namely, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol, in the range of 293.15−323.15 K. In addition, the effect of temperature and alkyl chain length of the alkanol on the excess molar volume and viscosity deviation of these mixtures has been thoroughly investigated and discussed. The results obtained are interpreted in terms of the structural changes that occur during mixing. Two approaches have been used to model the behavior of binary mixtures: the perturbed chain statistical associating fluid theory and free volume theory. Notably, satisfactory agreement between the experimental and calculated data derived from these models was observed. The average absolute deviations for the 1,3- dioxolane + 1-alkanol mixtures predicted by the PC-SAFT model were approximately 1.13, 1.06, 1.03, 1.08, and 1.11%, respectively. Moreover, the deviations between the experimental viscosities and their correlated values, as determined by the free volume theory, were consistently less than 3% for all binary mixtures studied.