Abstract Lithium iodide (LiI) as cathode for lithium-iodine (Li-I 2 ) batteries hold great promise compared to I 2 mainly owing to its greater merits, including its potential pairing with a lithium-metal-free anode and only ~5% decrease in theoretical capacity. LiI confined within the meso-micro porous carbon polyhedrons (LiI@MCP) as cathode for Li-I 2 batteries has been studied for the first time. Benefiting from the rich meso-/micro-porous structures and highly conductive frameworks of MCP, the LiI@MCP with uniform distribution of LiI displays high reversible capacity, good rate abilities and superior long cycling life at 2C over 800 cycles with a low capacity decaying rate (0.021% per cycle). This work will open a new paradigm for the use of LiI as cathode for high-performance Li-I 2 batteries.