A new class of mesoporous carbon polyhedrons (MCPs) with a facet-to-facet close-packed model are presented for the first time as electrode materials for electrochemical capacitors (ECs). These MCPs are evolved directly from the colloidal carbon microspheres (CCMs) by a new silica-free approach, the top-down carbonate (Li2CO3) site-occupying strategy. The obtained polyhedral materials consist of a desirable mesoporous structure with mesopores with a mean size of about 30 nm. The unique structures of the large-size mesopores in a close-packed combination are considered to provide a more favourable pathway for electrolyte penetration and transportation, as well as good electronic conductivity for electrochemical energy storage applications. Accordingly, the resultant mesoporous materials show great promise for high performance EC applications, of which high energy and high power properties are desirable.