In this study, multifunctional poly(acrylic acid) modified lanthanide-doped GdVO4 nanocomposites [PAA@GdVO4: Ln3+ (Ln ¼ Yb/Er, Yb/Ho, Yb/Tm)] were constructed by filling PAA hydrogel into GdVO4 hollow spheres via photoinduced polymerization. The up-conversion (UC) emission colors (green, red and blue) can be tuned by changing the codopant compositions in the matrices. The composites have potential applications as bio-probes for cell imaging. Meanwhile, the hybrid spheres can act as T1 contrast agents for magnetic resonance imaging (MRI) owing to the existence of Gd3+ ions on the surface of composites. Due to the nature of PAA, DOX-loaded PAA@GdVO4:Yb3+/Er3+ system exhibits pH-dependent drug releasing kinetics. A lower pH offers a faster drug release rate. Such character makes the loaded DOX easily released at cancer cells. The cell uptake process of drug-loaded composites was observed by using confocal laser scanning microscopy (CLSM). The results indicate the potential application of the multifunctional composites as theragnostics (effective bimodal imaging probes and pH-responsive drug carriers).