The phase equilibria in the subsolidus region of the La2O3-VO system are studied by different methods of physicochemical analysis (X-ray powder diffraction, differential thermal analysis, IR spectroscopy, and electrical resistivity and magnetic susceptibility measurements). It is established that the phase with the unit cell parameters close to those of LaVO3 is formed in this system. The homogeneity range of this phase is 22-27 mol % La2O3. The unit cell parameters of the phase are calculated in a wide range of concentrations. It is shown that the redistribution of oxygen between the coexisting phases and formation of centers containing vanadium(III) cations occur.