This work reports thermophysical properties measurements of binary mixtures of N,N-dimethylacteamide with 1-pentanol and 2-pentanol. Density, ρ, speed of sound, u, refractive index, nD, and kinematic viscosity,ν, were measured over the whole composition range at the temperatures (283.15, 298.15 and 313.15) K and at atmospheric pressure p = 0.1 MPa. Experimental data were used to calculate the following properties: excess molar volume, VE, excess isentropic compressibility,κSE, refractive index deviation, ΔnD, and viscosity deviation, Δη. These properties were correlated with mole fraction or volume fraction using the Redlich-Kister equation. Excess molar volumes were positive for both mixtures although there are some slight negative VE values for the system containing 1-pentanol at lower temperatures and at lower mole fractions. Refractive index deviation behaviour against composition for (N,N-dimethylacetamide + 1-pentanol) was sigmoidal at lower temperatures and negative at T = 313.15 K, on the other hand ΔnD values are negative for the mixture with 2-pentanol. Excess isentropic compressibilities and viscosity deviations were negative for the two systems. The results obtained were interpreted based on both structural and energetic effects. These results were further compared with our previous results for mixtures containing N,N-dimethylacetamide and several n-alkanols or 2-alkanols in order to understand both the influence of the hydrocarbon chain length and the hydroxyl group position.