A liquid carbon dioxide (l-CO2) based coating approach is developed for ultrathin, uniform, and conformal carbon coating of hierarchically mesoporous LiFePO4 (LFP) nano/microspheres for fabricating high-energy-density and high-power-density carbon coated LFP (C-LFP) with long-term cyclability. The unique properties of l-CO2 result in an ultrathin carbon layer (1.9nm) distributed all over the primary nano-sized LFP particles (20–140nm in diameter), forming a core (LFP)-shell (carbon) structure. This unique structure provides facile penetration of liquid electrolytes and rapid electron and Li-ion transport. C-LFP exhibits high reversible capacity, high energy and power density (168mAhg−1 at 0.1C, 109Whkg−1 and 3.3kWkg−1 at 30C, respectively) with excellent long-term cyclability (84% cycle retention at 10C after 1000 cycles). In addition, the ultrathin and uniform carbon layer of the mesoporous microspheres allows a high tap density (1.4gcm−3) resulting in a high volumetric energy density (458WhL−1 at a 30C rate). Furthermore, C-LFP presents a high capacity and stable cycling performance under low-temperature and high-temperature environment. Well-developed carbon coating approach in this study is simple, scalable, and environmentally benign, making it very promising for commercial-scale production of electrode materials for large-scale Li-ion battery applications.