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It is well known that molecular structure has great influence on the porous structure prepared by breath figures. However, the effect of graft architecture on porous structure from graft copolymer is unclear. Here, the cellulose-based graft copolymers with different graft architectures were synthesized and the highly ordered porous films were facilely prepared by breath figure method. The effects of graft architecture with four different structural parameters on porous structure were systematically investigated. It was found that the pore size increased with the increasing graft chain length, main chain length or molecular weight, while the pore size decreased with the increasing graft density under other similar structural parameters. The shorter main chain and the higher graft density resulted in the smaller pore size. Moreover, the shorter main chain was more beneficial for the formation of highly ordered porous structure than the longer main chain. These results will help to understand the effect of graft architecture on porous structure and regulate pore size by adjusting the graft architecture. [ABSTRACT FROM AUTHOR]