Abstract: Ordered mesoporous carbons were prepared by pyrolysis of polymer blends, which were formed by the organic-organic self-assembly of resorcinol-formaldehyde pre-polymers and tri-block copolymers under acidic conditions. The tri-block copolymer mixtures of F127 and P123 were used as structure-directing agents. The samples were characterized by X-ray diffraction, transmission electron microscopy and nitrogen adsorption. Results show that the degree of order of mesoporous carbons exhibits a maximum with increasing holding time from 24 to 72h. When the molar ratio of the F127 to P123 is 1, the mesoporous carbon obtained has the most ordered hexagonal mesostructure (P6mm), with a typical BET surface area of 640.34m2/g, pore size of 3.68nm and pore volume of 0.59cm3/g.