Experimental results are reported of excess molar volumes V-m(E) and excess molar enthalpies H-m(E) at T = 298.15 K for twelve binary mixtures of alkanols (ethanol, 1-butanol, or iso-butanol) or alkanes {n-heptane, iso-octane (2,2,4-trimethylpentane), or n-octane} with butyl-vinyl ether or iso-butyl-vinyl ether. A vibrating-tube densitometer was used to determine V-m(E). The quantity H-m(E) was measured by using a quasi-isothermal flow calorimeter. The results reveal the effects of molecular structure on the ability of an ether molecule to form (alkanol + ether) associates. The applicability of the ERAS model has been investigated for describing the thermodynamic excess properties.