In the development of energy-storage devices, simultaneously achieving high power and large energy capacity at fast rate is still a great challenge. In this paper, the synergistic effect of structure and doping in the graphene is demonstrated for high-performance lithium storage with ulftrafast and long-cycling capabilities. By an in situ constructing strategy, hierarchically porous structure, highly conductive network, and heteroatom doping are ideally combined in one graphene electrode. Compared to pristine graphene, it is found that the degree of improvement with both structure and doping effects is much larger than the sum of that with only structure effect or doping effect. Benefitting from the synergistic effect of structure and doping, the novel electrodes can deliver a high-power density of 116 kW kg(-1) while the energy density remains as high as 322 Wh kg(-1) at 80 A g(-1) (only 10 s to full charge), which provides an electrochemical storage level with the power density of a supercapacitor and the energy density of a battery, bridging the gap between them. Furthermore, the optimized electrodes exhibit long-cycling capability with nearly no capacity loss for 3000 cycles and wide temperature features with high capacities ranging from -20 to 55 °C.