Electroresponsive polymers are promising materials for touch-based technologies, electric armour, battery membranes and soft actuators especially because of the speed and ease of application of electrical stimuli to bulk polymers. While a wide range of electrically triggered actuator, sensor and harvester polymers have been developed, and electrically controlled adhesion between gels has been demonstrated, modification of bulk mechanical properties via electrical stimuli has remained elusive. Here, molecular dynamics simulations are used to present a new functional polyelectrolyte whose bulk mechanical properties (stiffness, yield stress and hardening modulus) can be enhanced with the application of electric field. Systematic investigation of nanostructure configuration established that the dominant mechanisms are reorientation of stretching of the polymer chains, which also extends the ionic clusters into necklace-like configurations that maintain strong electrostatic interactions throughout deformation. Study of electric field response for different architectures found that it is very sensitive to the distribution of charges – the charges must be tightly attached to the polymer backbone, and responsivity is greater if a single backbone contains both positive and negative charges. The insights provided by this work are a guide for future experimental realization of polymers with electric field regulated mechanical properties.