Ferroelectric macroporous poly(vinylidene fluoride-trifluoroethylene) membranes have been produced by isothermal crystallization from the solution at different temperatures starting from different diluted solutions of the co-polymer in dimethylformamide. In this way pore architecture, consisting in interconnected spherical pores can be obtained. The mechanism and kinetics of solvent evaporation was investigated and related to the evolution of the polymer microstructure. The mechanism underlying the pattern formation has been discussed on the light of the Flory-Huggins (FH) lattice theory, grain boundary effects and the Cahn-Hilliard equation for mass conservation systems. It was also observed that the temperature or initial concentration of the crystallization process does not affect the phase, ferroelectric transition temperature or the melting temperature of the polymer.