Multi-dimensional metal oxides have attracted great attention in diverse applications due to their intriguing performances, however the structural design remains challenging particularly in organic chelation chemistry. Although the metal-organic complex with different architectures have been reported, the structural formation mechanisms are still lack of understanding because of the complex chelating process. Herein, we introduce a new metal-organic coordination strategy to construct metal-decorated (Ni, Co, Mn) Mo-based compound from 2D nanopetal to 3D microflower for the first time. We find that the chelating process of metal-organic complex can be tuned by surfactant, and then give rise to different structures, where the metal can be further decorated and tuned. Thus, the metal (oxide) decorated MoO2/C-N with different structures were designed, enabling an extremely high lithium storage capability of 1018 mAh g-1 and rate capacities even at 10 A g-1 over 1000 cycles. In addition, the relations between the electrochemical behaviors and structures was analyzed by kinetic analysis, and then a high rate lithium ion battery is introduced using the Ni-MoO2/C-N and Nick-rich layered oxide as the anode and cathode, respectively. We believe this general metal-organic coordination strategy is applicable for other multi-functional materials for greater capabilities.