Double perovskite La2FeCrO6 (LFCO) powders were synthesized via the hydrothermal method, which crystallized in an orthorhombic (Pnma) structure and exhibited a spherical morphology with an average particle size of 900 nm. Fourier transform infrared spectroscopy demonstrated the presence of fingerprints of vibrational modes of [FeO6] and [CrO6] octahedra in the powders. The XPS spectra revealed dual oxide states of Fe (Fe2+/Fe3+) and Cr (Cr3+/Cr4+) elements, and the oxygen element appeared as lattice oxygen and defect oxygen, respectively. The LFCO powders exhibited weak ferromagnetic behavior at 5 K with a Curie temperature of 200 K. Their saturation magnetization and coercive field were measured as 0.31 μB/f.u. and 8.0 kOe, respectively. The Griffiths phase was observed between 200 K and 223 K. A butterfly-like magnetoresistance (MR)–magnetic field (H) curve was observed in the LFCO ceramics at 5 K with an MR (5 K, 6 T) value of −4.07%. The temperature dependence of resistivity of the LFCO ceramics demonstrated their semiconducting nature. Electrical transport data were fitted by different conduction models. The dielectric behaviors of the LFCO ceramics exhibited a strong frequency dispersion, and a dielectric abnormality was observed around 260 K. That was ascribed to the jumping of electrons trapped at shallow levels created by oxygen vacancies. The dielectric loss showed relaxation behavior between 160 K and 260 K, which was attributed to the singly ionized oxygen vacancies.