 We report a new class of high-capacity chalcogen–carbon composite negative electrodes for Na rechargeable batteries, consisting of tellurium-infiltrated ordered mesoporous carbon CMK-3. Its unparalleled electric conductivity makes Te a promising electrode material with high-capacity utilization. The rechargeable cell Na/Te@CMK-3, using a carbonate-based electrolyte, exhibited a large stable capacity of ~ 320 mA h (g-Te)−1 at 0.2 C with an excellent rate capability (55% of the theoretical specific capacity at 2 C-rate), and long-term cyclability (> 500 cycles), as well as 100% coulombic efficiency. Our study evidences the great potential of mesoporous carbon-encapsulated Te materials concepts as a new class of high-performance chalcogen-based electrode materials for Na rechargeable batteries.