Highly ordered porous membranes of cellulose triacetate (CTA) were prepared successfully on ice substrates using breath figure method. The pore size and structure of the membrane were modulated by changing CTA concentrations and substrate materials. As the CTA concentration in the casting solution increased, the pore size in the formed membrane decreased. The regularity of the membrane cast on the ice substrate was much better than that of the membrane cast on glass substrate, because the low temperature of ice substrate slowed down the evaporation rate of organic solvent, which offered enough time for condensed water droplets to self-organize into an ordered array dispersed in the polymer solution before their coagulation. The ordered porous CTA membrane was not only used for microfiltration, but also used for fabrication of functional microstructures. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 552-558