Experimental results are reported of excess molar volumes V,E and excess molar enthalpies H-m(E) at T = 313.15 K for twelve binary mixtures of alkanols (ethanol, l-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 using a quasi-isothermal flow calorimeter. The applicability of the ERAS model has been investigated for describing the thermodynamic excess properties at different temperatures. The results reveal the effect of the temperature and molecular structure on the ability of an ether molecule to form alkanol-ether associates.