A fascinating core–shell-structured graphitic carbon material composed of ordered microporous core and uniform mesoporous shell is fabricated for the first time through a site-specific chemical vapor deposition process by using a nanozeolite@mesostructured silica composite molecular sieve as the template. The mesostructure-directing agent cetyltrimethylammonium bromide in the shell of the template can be either burned off or carbonized so that it is successfully utilized as a pore switch to turn the shell of the template “on” or “off” to allow selective carbon deposition. The preferred carbon deposition process can be performed only in the inner microporous zeolite cores or just within the outer mesoporous shells, resulting in a zeolite-like ordered microporous carbon or a hollow mesoporous carbon. Full carbon deposition in the template leads to the new core–shell-structured microporous@mesoporous carbon with a nanographene-constructed framework for fast electron transport, a microporous nanocore with large surface area for high-capacity storage of lithium ions, a mesoporous shell with highly opened mesopores as a transport layer for lithium ions and electron channels to access inner cores. The ordered micropores are protected by the mesoporous shell, avoiding pore blockage as the formation of solid electrolyte interphase layers. Such a unique core–shell-structured microporous@mesoporous carbon material represents a newly established lithium ion storage model, demonstrating high reversible energy storage, excellent rate capability, and long cyclic stability.