In this work, a new and facile strategy is developed to synthesize a single-phase Eu3+-doped mesoporous gadolinium oxide nanorods (MS-Gd2O3:Eu@PEG) by incorporating a facile wet-chemical route, which includes an induced silica layer being coated onto the nanorods, and evolution of pores and formation of channels, as well as a surface-modified process for multimodal imaging and anti-cancer drug delivery. The properties of these as-prepared Gd2O3:Eu nanorods are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), N-2 adsorption/desorption, and photoluminescence (PL). The in vitro cytotoxicity test, drug loading, and drug release experiments reveal that the MS-Gd2O3:Eu@PEG nanorods have good biocompatibility, efficient loading capacity, and pH-sensitive releasing behavior, suggesting the nanorods could be an ideal candidate as drug delivery vehicles for cancer therapy. Furthermore, the MS-Gd2O3:Eu@PEG nanorods show clearly dose-dependent contrast enhancement in T-1-weighted magnetic resonance images and can potentially be used as a T-1-positive contrast agent. These results indicate our prepared multifunctional mesoporous gadolinium oxide nanorods can serve as a promising platform for simultaneous anticancer drug delivery and multimodal imaging.