Excess solar volumes V-E for binary liquid mixtures of (n-alkanol + 2,5-dioxahexane, 2,5,8-trioxanonane, 2,5,8,11-tetraoxadodecane, 3,6,9-trioxaundecane, or 5,8,11-trioxapentadecane) have been measured as a function of compositions using a continuous dilution dilatometer at 298.15 K and atmospheric pressure over the full range of compositions. The n-alkanols were methanol, ethanol, 1-butanol, and 1-pentanol. The results have been used to estimate the excess partial molar volumes of the components. The V-E for each of the mixture studied are negative with the exception of 1-pentanol + 2,5,8-trioxanonane or 2,5,8,11-tetraoxadodecane and change sign for 1-butanol + 2,5-dioxahexane over the whole composition range. For each case, the V-E increases as the chain length of the iz-alkanol increases.