Fe3O4 nanoparticles with ultrasmall sizes show good T1 or T1+T2 contrast abilities, and have attracted considerable interest in the field of magnetic resonance imaging (MRI) contrast agents. For effective biomedical applications, the colloidal stability and biocompatibility of the Fe3O4 nanoparticles need to be improved without reducing MRI relaxivity. In this paper, star polymers were used as coating materials to modify Fe3O4 nanoparticles in view of their dense molecular architecture with moderate flexibility. The star polymer was composed of a β-cyclodextrin (β-CD) core and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) arms. Meanwhile, reduced glutathione (GSH), as a model drug, was also associated with the star polymer. Thus, a new platform for simultaneous diagnosis and treatment was achieved. Compared to the Fe3O4 nanoparticles coated with linear polymers, the Fe3O4 nanoparticles coated with star polymers (Fe3O4@GCP) possessed higher GSH association capacity and better stability in serum-containing solution. GSH could be released from Fe3O4@GCP nanoparticles in response to pH value of the solution. Since the sulfhydryl group on GSH is able to combine free radicals, Fe3O4@GCP nanoparticles exhibited less cytotoxicity compared to the Fe3O4 nanoparticles without including GSH. Furthermore, the nanoparticles could also serve as good T1 MRI contrast agent, and the MRI relaxivity of Fe3O4@GCP nanoparticles did not decrease after coated with the star polymer. These results indicate that the precisely designed Fe3O4@GCP nanoparticles could be used as a versatile promising theranostic nano-platform.