We proposed here a one-pot route to prepare resorcinol/formaldehyde (RF) resin-based carbon materials with highly ordered mesostructures in an aqueous media. Compared with other techniques, the synthesis is a single-step process; neither prepolymerization nor thermal solidification is needed. The crucial difference to the previous methods is that the commonly used formaldehyde is replaced with hexamine. Hexamine can serve as a release source of formaldehyde to control the kinetics of RF polymerization reaction. The combined use of resorcinol and hexamine allows the accelerated synthesis without disturbing the cooperative self-assembly of RF resin and amphiphilic triblock copolymer. A mesophase transformation from body-centered cubic (Im3m) to 2-D hexagonal (p6m) structure can be achieved by simply adding 1,3,5-trimethylbenzene to the synthesis. Especially, this synthesis can be performed not only under weakly basic conditions but also under highly acidic conditions, despite that the acid-catalyzed synthesis will result in the formation of the product with a relatively low thermal stability.