Polyoxometalate (POM) -based metal–organic framework (MOF) -derived Co3O4/CoMoO4 nanohybrids were successfully fabricated by a facile solvothermal method combined with a calcination process, in which a Co-based MOF, i.e. ZIF-67 acts as a template while a Keggin type POM (H3PMo12O40)serves as a compositional modulator. The materials were characterized through SEM, XRD, TEM, EDS mapping and electrochemical measurements, respectively. When the Co3O4/CoMoO4 nanohybrids were applied as the anode materials for lithium-ion batteries (LIBs) , it displays large lithium storage capacity (around 900 mAh g-1 at 0.1 A g-1), high cycling stability, and it can also exhibit good rate performances. This work might throw some lights on the POM-based MOF host-guest synthesis strategy on the preparation of polymetallic oxides for enhanced electrochemical energy storage and further applications.