Low cargo-loading capacity and inadequate stability have severely retarded the clinical translation of micellar nanomedicines. Herein, we present a nanosystem prepared by self-assembly of doxorubicin (DOX) and Fe2+ with drug-metal coordination interactions, followed by a surface decoration of multiarmed PEG-dipyridine. The micellar nanoparticles possessed high drug-loading capability and stability in physiological conditions. Results showed that nanoparticles facilitated the intracellular codelivery of Fe2+ and DOX. Moreover, intracellular overload of Fe2+ significantly enhanced the generation of ROS via the Fenton reaction. This strategy provides a facile method of preparing metal coordinated micellar nanoparticles for synergistic chemo/chemodynamic therapy.