We report on the atomic ordering of B-site transition-metals and magnetic properties in double-perovskite oxides, La2CrFeO6 (LCFO) and La2VMnO6 (LVMO), which have never been reported to exist in ordered forms. These double-perovskite oxides are particularly interesting because of possible ferromagnetism (expected from the Kanamori-Goodenough rule for LCFO) and half-metallic antiferromagnetism (predicted for LVMO). Using pulsed-laser deposition technique with single solid-solution targets, we have prepared epitaxial films in ordered forms. Despite similar ionic characters of constituent transition-metals in each compound, the maximum B-site order attained was surprisingly high, ∼90% for LCFO and ∼80% for LVMO, suggesting a significant role of epitaxial stabilization in the spontaneous ordering process. Magnetization and valence state characterizations revealed that the magnetic ground state of both compounds was coincidently ferrimagnetic with saturation magnetization of ∼2μ
Bper formula unit, unlike those predicted theoretically. In addition, they were found to be insulating with optical band-gaps of 1.6 eV and 0.9 eV for LCFO and LVMO, respectively. Our results present a wide opportunity to explore novel magnetic properties of binary transition-metal perovskites upon epitaxial stabilization of the ordered phase.