Physico-chemical effects present in five binary liquid mixtures containing n-butyl acetate + a homologue series of 1-alkanols have been studied over the full range of concentrations by measuring the density and viscosity at temperatures 293.15 to 323.15 K. The alcohols considered are those from 1- hexanol up to 1-decanol. Excess molar volumes are positive for all binary mixtures over the whole concentration range, while viscosity deviations are negative for all binary systems. Influences of temperature and addition of −CH2 group of alcohols on excess properties have been discussed. Systems involving n-butyl acetate + 1-alkanol are mainly characterized by the self-association of the alcohol, and the mentioned effect decreases when the size of the 1-alkanol increases in the mixtures. As a result, molecular interactions are weaker in longer 1-alkanols. Moreover, the applicability of PC-SAFT theory has been examined and discussed for these systems. Although the PC-SAFT model provides consistent results on the thermal expansion coefficients, α in the studied mixtures, for better prediction of the excess molar volumes of mentioned solutions, more complex mixing rules or more adjustable parameters should be used.