Many efforts have been devoted towards the fabrication of multifunctional (mesoporous, magnetic and fluorescent) nanocomposites due to their growing applications as adsorbents, catalysts, and biomedical application, etc. Novel, flower-structured multifunctional Fe3O4/YVO4:Eu(3+)@SiO2 microspheres were successfully synthesized through a simple self-assembled process. The as-obtained products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, photoluminescence (PL) spectroscopy and using a vibrating sample magnetometer (VSM). The results reveal that the novel composites exhibit typical mesoporous structure, narrow size distribution, good monodispersity, excellent luminescent properties and superparamagnetic features. The effects of magnetic field on the luminescent intensity of multifunctional composites have been discussed in our manuscript. Furthermore, the adsorption experiments indicate that the resulting multifunctional composites are powerful adsorbents for the removal of methylene blue from water with a maximum adsorption efficiency of 98%. It is envisioned that multifunctional composites with high surface area are of particular interest for adsorption of pollutants, separation, and water purification.