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40 Li2O–5 WO3–(55-[Formula: see text]) B2O3: [Formula: see text]V2O5 (mol%) for [Formula: see text] glasses were prepared by melt-quenching. Electric polarization was described in terms of the dielectric constant ([Formula: see text]) and loss ([Formula: see text]). Mixed conduction phenomenon was explained by redox pairs [Formula: see text] and [Formula: see text] at high temperatures. Electronic polarizability ([Formula: see text]) was determined over a range of frequencies (100[Formula: see text]Hz–100[Formula: see text]kHz) and temperatures (30–[Formula: see text]C). The change of boron coordination in the glass network was explained with the aid of temperature coefficient of polarizability ([Formula: see text]). Nonlinear susceptibility ([Formula: see text]) and optical band gap ([Formula: see text]) were studied as a function of concentration of V2O5. The highest values of [Formula: see text] and [Formula: see text] were obtained at [Formula: see text][Formula: see text]mol%. These glasses may find potential practical applications in the fields of solid-state ionics and nonlinear optics.