Mesoporous carbons with different mesostructures were prepared with amphiphilic triblock copolymer PlurionicF127, Pluronic P123 and blends of F127/P123 as templates, and hexamethyltetramine cured novolac as precursors. When the mass ratio of template/novolac changed from 1/1 to 1/2, the ordering of mesoporous carbons reduced, and mesoporous carbons prepared with F127 as templates exhibited more excellent ordering compared to those prepared with P123 as templates. Increasing the content of P123 in the blends of F127/P123 induced the changes of mesophase and texture properties of resulting products. When the mass ratio of F127/P123 decreased from 0.67/0.33 to 0.33/0.67, the mesoporous carbons changed from two dimensional (2D) hexagonal to wormhole framework. Meanwhile, the mesoporous carbons exhibited similar surface area (about 574 cm2/g), and decreasing pore size (from 3.4 to 3.0 nm), total pore volume (0.37–0.32 cm3/g), d-spacing (8.3–7.7 nm) and wall thickness (5.5–3.9 nm). The 2D hexagonal mesoporous carbons prepared with F127 as templates exhibited larger specific surface area (670 m2/g), pore size (3.5 nm) and total pore volume (0.40 cm3/g), and slightly lower d-spacing (7.4 nm) and wall thickness (5.0 nm) compared to those prepared with blends of F127/P123 as templates.