Er3+/Yb3+ co-doped BaMoO4 (BaMoO4:Er3+/Yb3+) composites with superparamagnetic iron oxide nanoparticles (SPIONs) incorporated were successfully synthesized by a cyclic microwave-assisted metathetic (MAM) method followed by heat-treatment. The microstructure exhibited well-defined and homogeneous morphology with the BaMoO4:Er3+/Yb3+ particle size of 1-2 μm and Fe3O4 particle size of 0.1-0.5 μm. The Fe3O4 particles were self-preferentially crystallized and immobilized on the surface of BaMoO4:Er3+/Yb3+ particles. The synthesized SPION/BaMoO4:Er3+,Yb3+ composites were characterized by X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Optical properties were examined using photoluminescence emission measurements and Raman spectroscopy.