structured nanoprobe that incorporates water-soluble silica and water-interacted gadolinium oxide, endowed with excellent hydrophilicity and high magnetic resonance imaging (MRI) relaxivity. The nanoprobes are monodispersed and uniformed with a superior stability due to the formation of Gd−O−Si bonds. The nanoprobe possesses an MRI relaxivity of 39.08 mM −1 s −1 , 9.3 times that of clinical Gd chelates, gaining a significant MRI enhancement in vivo; the classical Solomon− Bloembergen−Morgan theory is applied to explicate the relaxation enhancement mechanism. Multicolor and enhanced emissions are tunable through adjusting Yb 3+ /Li + -doping concentrations in Gd 2 O 3 :Yb 3+ /Er 3+ /Li + . A theoretical model based on the rate equations of upconversion energy-transfer processes is established to address the nanoprobe's photoluminescence. Cross-linked with folate-PEG, the nanoprobe can be absorbed by nasopharyngeal, cervical, and breast carcinoma cells, rendering a vivid multicolor living cell imaging. The nanoprobe owns a negligible nanotoxicity according to in vitro cytotoxicity and in vivo immunotoxicity, histopathology, and hematology assays. This study demonstrates that folate-PEGylated SiO 2 @Gd 2 O 3 :5%Yb 3+ /2%Er 3+ /6%Li + core@dotted-shell nanoprobes designated for multimodal imaging can achieve simultaneously enhanced MR relaxivity, photoluminescence efficiency, tumor-targeting ability, and biocompatibility. Both designing of nanoprobe and addressing MR/photoluminescence enhancement mechanism facilitate the development of practical multimodal imaging nanoprobes for accurate diagnosis of early tumors.