Lithium niobate (LN) films have been obtained on pure congruent single-domain LN substrates by the liquid phase epitaxy technique. Li-rich flux of LiVO3 has been used. The optimum temperature for the film preparation has been found to be 860 degreesC. Raman and photoluminescence microspectroscopy were used to analyse the Li/Nb ratio, which decreases along the film depth, and the vanadium concentration, which increases along the film depth.