Mondispersed submicrometer GdPO4:Eu3+ hollow spheres were synthesized via an effective one-pot hydrothermal process. These hollow spheres have the average diameter of 200 nm, and the shell thickness is about 20 nm. The surface of the spheres consists of a number of nanorods with diameters of about 10 nm and lengths of about 50-80 nm. Both magnetic and luminescent properties of the obtained Eu3+-doped GdPO4 hollow spheres were investigated. The hysteresis plot (M-H) analysis result indicates their paramagnetic property. The fluorescence spectra demonstrate that they emit orange-red color light originated from the D-5(0) -> F-7(J) transitions of the Eu3+ ions. Therefore, the obtained GdPO4 hollow spheres hold promise for encapsulate drugs with controlled release. Moreover, the GdPO4:Eu3+ hollow spheres are attributes for bimodal magnetic resonance imaging (MRI)/optical bioimaging labeling.