The mid-range structure of glasses of the glass-forming system xNb(2)O(5)-(60 - x)P(2)O(5)-40Na(2)O, with x varying from 0 to 40, has been investigated by Raman spectroscopy and electro-optical Kerr measurements. It was found that the mid-range inhomogeneities in the glasses under study vary with x and their compositions and structures dramatically differ from the gross glass composition. It is shown that inhomogeneities with the 8NaNbO(3) + (Nb(2)O(5)·P(2)O(5)) composition are responsible for the electro-optical sensitivity of the glasses. The electro-optical structural elements of the inhomogeneities of this type are assumed to be fragments of the quasicubic lattice of crystalline NaNbO(3) demonstrating a rather high electro-optic Kerr coefficient. The obtained results are discussed in terms of the concepts of constant stoichiometric groupings and crystal motifs.