Large-scale octahedral Fe3O4 nanocrystallines with crystalline size of 100-500 nm were synthesized by a facile solvent-thermal method for electromagnetic wave application. The Fe3O4 nanocrystallines showed a higher saturation magnetization (M (s) ) value of 86.8 emu/g and larger coercivity (H (cj) ) value of 255 Oe than that of magnetite polycrystallines because of their good crystallization and dispersion. The epoxy resin composites with 40 vol% Fe3O4 powders provided good electromagnetic wave absorption performance (RL < -20 dB) in the range of 2.0-4.3 GHz over the absorber thicknesses of 3.5-6.8 mm. A minimum RL value of -47 dB was observed at 3.1 GHz with a thickness of 4.8 mm.