Ultra-high loading Co3O4 nanoparticles (NPs) with the particle size of ca. 10nm anchoring on the acid-sonication pretreated graphene oxide with induced in-plane vacancies (deGO) are in-situ synthesized through a low-temperature hydrothermal reaction. These in-plane vacancies can act as active sites for the formation of Co3O4 NPs since Co2+ ions have a strong bonding effect with the carboxylate groups decorating the defect edge sites, in which nucleation, growth and crystallization of Co3O4 NPs are well separated and confined in a several nanometer region. Although the content is extremely low (7wt%), deRGO can not only provide a support for anchoring Co3O4 NPs and work as a conductive matrix enabling good contact between them, but also prevent the particle aggregation and keep the integrity of the composite during long-term cycles. The as-prepared deRGO/Co3O4 anode exhibits a high specific capacity and superior rate performance with charge capacities of 727.1mAhg−1 at 2 C, 559.4mAhg−1 at 5 C and 70.45mAhg−1 at 30 C. Meanwhile, no capacity fade can be observed after 100 cycles at 1 C, revealing a stable cycling ability. Therefore this material has great potential application for advanced Li-ion batteries.