The1H-NMR spectra of liquid binary mixtures, N, N-dimethylformamide (DMF)-benzyl alcohol (PhCH2OH), were recorded at 298 K within whole range of the mixed solvent compositions. From these data were found the values of the spectral parameter, Δδ(DMF-PhCH2OH). The densities (d12) and viscosities (n12) of the mixed solvents were measured at 298.15 K, as well as the dielectric permittivities (ε12) at 293.15 K, 298.15 K, 303.15 K, 308.15 K, 313.15 K and 318.15 K. From all these new parent data, the values of molar volumes (V12), kinematic viscosities (n12/d12) and their deviations from “ideality” were calculated. Additionally, the values of the temperature coefficients of dielectric permittivity (α12), were found. The molar limiting conductances (A0) of NaCl were measured at 298.15 K within whole range of mixed solvent compositions. From these data were found the values of the association constants (KA) and the Walden products (A0·n). The scrutiny of all these structural parameters as functions of the mixture composition points at a formation of the “complexes” (sub-units) of the DMF · PhCH2OH and DMF · 2 PhCH2OH types in the bulk of the mixed solvents.