We report the stabilization of the B-site-ordered phase of epitaxial La2VMnO6 double-perovskite films grown by pulsed-laser deposition. Previous theoretical calculation predicted the possibility of realizing a spin-compensated half-metallic state in this system with an Mn3+ ion at a low spin state. In contrast, our magnetic measurements suggest that the system in ordered phase is ferrimagnetic with Mn3+ at a high spin state. Synchrotron radiation photoemission measurement indicates that the electronic ground state of this material is insulating: occupied Mn 3d t2g, Mn 3d eg, and V 3d t2g states are located far from the Fermi level. The optical band gap is estimated to be about 0.9 eV, which is similar to the charge transfer gap of LaMnO3 based on the optical absorption spectra.