increasing requirement of energy density. Among these alternatives to the conventional lithium-ion batteries, lithium-sulfur (Li-S) batteries are of particular interest due to their high theoretical gravimetric energy density (2500 Wh kg −1 ) and natural abundance of sulfur. [1] Selenium (Se), as an element that also belongs to the chalcogen group in periodic table, has been recently proposed as a promising cathode material. [2][3][4][5] In spite of the lower theoretical gravimetric capacity of Se (675 mAh g −1 ), the volumetric capacity of Se (3253 mAh cm −3 ) is comparable to that of S (3467 mAh cm −3 ). Moreover, Se possesses an electronic conductivity that is ≈20 orders of magnitude higher than S, which enables a higher utilization rate, better kinetics and higher loading of active materials in electrode. These advantages make Se a promising candidate of cathode materials for high energy lithium battery.The Li-Se electrochemistry highly depends on the organic electrolyte. In ether-based electrolytes, the Se cathode operated via solidliquid-solid mechanism suffers from the dissolution of reaction intermediates-lithium polyselenide, resulting in the continuous leakage of active materials and shuttle reaction between cathode and anode. [4][5][6] Using the carbonate-based electrolytes that seldom dissolve lithium polyselenide intermediates is a potential strategy to address this problem occurred in Li-Se batteries. [7] However, because of the irreversible reactions between the nucleophilic long-chain polysulfide anions (Se 2− or Se 2− ) and carbonate molecules, the bulk Se cathode even prepared with nanostructured Se active materials is incompatible with these electrolytes. [5,8,9] Recently, it was found that the Se confined in CMK-3 matrix can perform well with carbonate electrolytes. [2] By forming the space-confined Se chains in pores of carbon hosts, the Se molecules can are directly converted to Li 2 Se without the lithium polyselenide intermediates. [10] Moreover, the terminal Se molecules in helical Se x are preferentially attacked by Li + , enabling a higher electrochemical activity than the ring structure. [11] Inspired by this work, various carbon hosts have also been demonstrated for Li-Se batteries. Compared to the mesoporous carbon/Se (MeC/Se) [12][13][14] and hierarchical porous carbon/Se cathodes, [15][16][17] the MiC/Se cathodes such as metal-organic framework-derived MiC, [18][19][20] graphitic MiC Embedding the fragmented selenium into the micropores of carbon host has been regarded as an effective strategy to change the Li-Se chemistry by a solid-solid mechanism, thereby enabling an excellent cycling stability in Li-Se batteries using carbonate electrolyte. However, the effect of spatial confinement by micropores in the electrochemical behavior of carbon/selenium materials remains ambiguous. A comparative study of using both microporous (MiC) and mesoporous carbons (MeC) with narrow pore size distribution as selenium hosts is herein reported. Systematic investigations reveal that the high Se ut...