Porous graphene films are attractive as a gas separation membrane given that the selective layer can be just one atom thick, allowing high-flux separation. A favorable aspect of porous graphene is that the pore size, essentially gaps created by lattice defects, can be tuned. While this has been demonstrated for postsynthetic, top-down pore etching in graphene, it does not exist in the more scalable, bottom-up synthesis of porous graphene. Inspired by the mechanism of precipitation-based synthesis of porous graphene over catalytic nickel foil, we herein conceive an extremely simple way to tune the pore size. This is implemented by increasing the cooling rate by over 100-fold from -1°C-min(-1) to over -5°C s(-1). Rapid cooling restricts carbon diffusion, resulting in a higher availability of dissolved carbon for precipitation, as evidenced by quantitative carbon-diffusion simulation, measurement of carbon concentration as a function of nickel depth, and imaging of the graphene nanostructure. The resulting enhanced grain (inter)-growth reduces the effective pore size which leads to an increase of the H-2/CH4 separation factor from 6.2 up to 53.3.