Ordered mesoporous (2-50 nm) carbon films were fabricated using cooperative self-assembly of a phenolic resin oligomer with a novel block copolymer template (poly(styrene-block-N,N-dimethyl-n-octadecylamine p-styrenesulfonate), (PS-b-PSS-DMODA)) synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Due to the high Tg of the PS segment and the strong interactions between the phenolic resin and the PSS-DMODA, the segmental rearrangement is kinetically hindered relative to the cross-linking rate of the phenolic resin, which inhibits long-range ordering and yields a poorly ordered mesoporous carbon with a broad pore size distribution. However, relatively short exposure (2 h) to controlled vapor pressures of methyl ethyl ketone (MEK) yields significant improvements in the long-range ordering and narrows the pore size distribution. The average pore size increases as the solvent vapor pressure during annealing increases, but an upper limit of p/p0 = 0.85 exists above which the films dewet rapidly during solvent vapor annealing. This approach can be extended using mesityl oxide, which has similar solvent qualities to MEK, but is not easily removed by ambient air drying after solvent annealing. This residual solvent can impact the morphology that develops during cross-linking of the films. These results illustrate the ability to fine-tune the mesostructure of ordered mesoporous carbon films through simple changes in the processing without any compositional changes in the initial cast film.