Excess molar enthalpies, H-m(E), and excess molar volumes, V-m(E), have been determined at 298.15 K and at atmospheric pressure for the binary mixtures containing 1,3-dioxolane + four pairs of structural isomers of alkyl alkanoates, namely, propyl ethanoate and ethyl propanoate, butyl ethanoate and ethyl butanoate, pentyl ethanoate and ethyl pentanoate, and hexyl ethanoate and ethyl hexanoate, respectively. H-m(E,) values are always positive and increase as the chain length of the alkanoate is increased, showing maximum values varying from 153 J mol(-1)(propyl ethanoate) to 557 J mol(-1)(hexyl ethanoate). In contrast, V-m(E),values are positive in mixtures containing ethyl hexanoate, hexyl ethanoate, ethyl pentanoate, and pentyl ethanoate and negative for propyl ethanoate and ethyl propanoate, showing an inversion of sign for ethyl butanoate and butyl ethanoate. V-m(E) values vary from -0.07 cm(3) mol(-1) (propyl ethanoate) up to 0.18 cm3 mol(-1)(ethyl hexanoate), increasing as the chain length of the alkanoate is increased. Experimental data have been correlated using the Redlich-Kister equation.