A self-assembly process prepared needle-like crystals at room temperature. Calcination and temperature-programmed carburization processes facilitated an evolution of the as-prepared crystals into hollow, needle-like mesoporous tungsten carbide (WC). This synthesized, large-sized (approximately 3 mm) WC exhibited a highly specific surface area (9.74 m(2)/g). Moreover, the mesopores were centered at 20.2 nm for its advanced formation, and these could further enlarge to 34.2 nm via direct carburization. The successful synthesis of the materials is associated with the formation of a pre-assembled precursor with increased volatilized components and needle-like structure. Various pore evolutions during the synthesizing processes were discussed to explain the formation of mesostructures. The H-2 adsorption/desorption highly improves with the introduction of the mesoporous structure. The synthesized, needle-like WCs with mesoporous structure may be potential candidates for catalytic and adsorptive applications. (C) 2012 Elsevier B.V. All rights reserved.