A novel magnetic Ce(III) ion-imprinted polymer (Ce(III)-MIIP), grafted on organic-inorganic hybrid monolithic vinyl functionalized Fe3O4 (Fe3O4@HM), was synthesized for the first time by using the surface ion imprinting technology, in which Ce(III) was used as the template ion and acrylamide as the functional monomer. After the synthesized nanocomposites were well characterized, some parameters such as pH, adsorption time, eluent type, elution time and eluent volume, which affects the efficiency of magnetic solid phase extraction (MSPE), were studied in the determination of Ce(III). Under the optimized experimental conditions, Ce(III)-MIIP nanoparticles were used as the MSPE matrix, followed by inductively coupled plasma mass spectrometry (ICP-MS) determination with excellent selectivity, strong anti-interference ability, low mass transfer resistance and high adsorption capacity. The limit of detection, enrichment factor and adsorption capacity were 0.008 μg·L?1, 25 and 67.8 mg·g?1, respectively. The protocol was validated by analyzing certified reference materials and spike recoveries of complex environmental and mineral samples with satisfactory results. The relative standard deviations for the real samples were 1.7%~7.0%. In view of the advantages of facile preparation, fast adsorption rate, excellent selectivity and high adsorption capacity to Ce(III), the hybrid monolith-assisted Ce(III)-MIIP-based MSPE-ICP-MS protocol is promising for the determination of cerium in real environmental and mineral samples.