AbstractIn this work, an electric field is incorporated during the solvent evaporation step of the block copolymer self‐assembly and nonsolvent induced phase separation (SNIPS) process. This study investigates the structure of nonsolvent‐quenched polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) and polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer solutions after exposure to electric fields during solvent evaporation. The results indicate an emphasizing effect of the electric field, enhancing self‐assembly and compensating mediocre experimental parameters to a certain degree. However, the impact is found to be different for the two diblock copolymer membranes depending on the selection of experimental parameters as well as the segregation strength of the systems. In addition, an increasing length of the vertically aligned cylindrical pores by the electric field is observed for both membranes, scaling with the applied voltage. This effect is primarily attributed to the suppression of defects and ill‐alignment of polymer domains in the course of structure formation during SNIPS by the electric field. Scanning electron microscopy is used to image the surface and cross‐sectional morphology of the integral asymmetric membranes.