Electroactive macroporous poly[(vinylidene fluoride)-co-trifluoroethylene] membranes have been produced by solvent evaporation at room temperature, starting with a diluted solution of the copolymer in dimethylformamide. The pore architecture consists of interconnected spherical pores. This architecture is independent of the membrane thickness. The thickness of the membranes ranges from a few to several hundred mm, using spin coating and evaporation in static conditions, respectively. The pore structure is explained by a spinodal decomposition of the liquid/liquid phase separation and crystallization in the copolymer-rich phase.© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.