The Snoek relaxation profiles for ternary Niobium-Vanadium-Oxygen systems were analyzed by an embedded-cell model of statistical mechanics treatment. The relaxation characteristic and broadening mechanism were systematically discussed and some conflicting interpretations in the early research were clarified. The complicated Snoek spectrums of the Nb-V- O system can be resolved into a series of effective elementary Debye peaks, which result from the transitions of interstitial oxygen atoms between adjacent octahedral sites. The relaxation parameters of each elementary peak can be determined by element species and atomic arrangements within the corresponding embedded octahedron. The Snoek relaxation characteristic in Nb-V-O systems mainly depends on the sites distributions and the transitions status of the interstitial oxygen atoms, which are controlled by the site-dependence energies and the transition probabilities, respectively.