A series of vanadium-containing mesoporous carbon catalysts were synthesized by the co-assembly method using phenolic resol, vanadyl acetylacetonate [VO(acac)(2)], and Pluronic F127 as carbon source, metal source, and template, respectively. The effects of the calcination temperature on the transformation of vanadium species and the carbon framework were investigated. During the calcination treatment, the nanoparticles of vanadium species mainly confined in the carbon matrix were formed along with the further cross-linking and carbonization of the phenolic resol network. The obtained catalysts exhibited the two-dimensional hexagonal mesostructures, high surface areas, and uniform pore sizes. Their catalytic activity in the benzene hydroxylation reaction was tested and the 0.2-V-C-600 catalyst showed the high performance with the benzene conversion of 31.8% and phenol selectivity of 94.9% as well as the good stability in recycles. (C) 2014 Elsevier B.V. All rights reserved.