Mixtures of a linear or cyclic ether + CCl4 have been studied using the Flory model and the Kirkwood-Buff integrals formalism. The relative variation of the molar excess enthalpy, H-m(E), along the homologous series of the investigated systems was investigated in terms of the contributions to HmE from the breaking of the ether ether and CCl4-CCl4 interactions upon mixing and the formation of ether-CCl4 interactions. For CH3(CH2)(u-1)O(CH2CH2O)(v)(CH2)(u-1)CH3 + CCl4 mixtures, an increase in u (v = 0) leads to a weakening of interactions between unlike molecules. In contrast, an increase in v (u fixed) or cyclization leads to stronger interactions between unlike molecules. For acetal mixtures, proximity effects weaken this type of interaction. From the application of the two models, it is shown that the structure of the mixtures is close to that of random mixing. Erroneously, strong orientational effects are predicted by the Flory model for 1,3-dioxolane or 1,3-dioxane + CCl4 systems, but this is because the theory cannot describe asymmetric H-m(E) curves when the mixture compounds have similar values for V-i (molar volume) and for V-i* (reduction parameter for volume). The Flory results on the excess molar volumes are discussed in terms of the interactional, curvature, and P* contributions to this excess function.