Deoxynivalenol-3-glucoside (D3G), the masked form of the important mycotoxin deoxynivalenol (DON), displays potential toxicity but is difficult to control owing to the lack of rapid detection methods. Herein, an innovative molecularly imprinted polymer (MIP)-based electrochemical sensor was developed for the rapid detection of D3G. MIP, an efficient recognition element for D3G, was electropolymerized using o-phenylenediamine based on a surface functional monomer-directing strategy for the first time. CeO2, which contains both Ce3+ and Ce4+ oxidation states, was introduced as a nanozyme to catalyze H2O2 reduction, while Mn doping generated more oxygen vacancies and considerably improved the catalytic activity. Mn-CeO2 also served as a promising substrate material because of its large surface area and excellent conductivity. Under optimal conditions, a good linear relationship was observed for D3G detection over the concentration range of 0.01-50ng/mL. The proposed sensor could detect D3G down to 0.003ng/mL with excellent selectivity, even distinguishing its precursor DON in complex samples. The sensor exhibited acceptable stability with high reproducibility and accuracy, and could successfully determine D3G in grain samples. To the best of our knowledge, this is the first electrochemical sensing platform for rapid D3G detection that can easily be expanded to other masked mycotoxins.