The structure of ordered mesoporous carbons fabricated using poly(styrene-block-N,N,-dimethyl-n-octadecylamine p-styrenesulfonate) (PS-b-PSS-DMODA) as the template and phenolic resin (resol) as the carbon source can be easily manipulated by inclusion of low concentrations of low volatility selective solvents in the casting solution. Casting from neat methyl ethyl ketone yields a disordered structure even upon thermal annealing. However, addition of both dioctyl phthalate (DOP, PS selective) and dimethyl sulfoxide (DMSO, resol and PSS-DMODA selective) at modest concentrations to this casting solution provides sufficient mobility to produce highly ordered films with cylindrical mesopores. The DOP acts to swell the hydrophobic domain and can more than double the mesopore size, while the DMSO acts to swell the resol phase. Moreover, the surface area of the mesoporous carbons increases significantly as the meosopore size increases. This is a result of the decrease in wall thickness, which can be ascertained by the constant d-spacing of the mesostructure as the pore size increases. This behavior is counter to the typical effect of pore swelling agents that increase the pore size and decrease the surface area. Moreover, with only 4 wt % DOP/DMSO in the solution (20 wt % relative to solids), the scattering profiles exhibit many orders of diffraction, even upon carbonization, which is not typically observed for soft templated films. Variation in the concentration of DOP and DMSO during casting enables facile tuning of the structure of mesoporous carbon films.