Inspired by the electromigration phenomenon in biomolecules, we have developed oligoamine-modified polyacrylonitrile (PAN) particles to achieve a negative ER effect. Our study shows that short oligoamine-modified PAN exhibits a positive ER effect due to improved dielectric properties, while long oligoamine-modified PAN demonstrates a negative ER effect thanks to enhanced electrophoretic force. This breakthrough allows for controlled acquisition of the negative ER effect, differing from previous trial-and-error methods. These negative ER particles migrate toward the anode in DC electric fields, mirroring the electromigration seen in biomolecules. Our research offers a new strategy for developing both positive and negative ER materials, potentially benefiting various industries.