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Relaxor ferroelectric polymers exhibit both high dielectric constants and low remnant polarization and thus deliver much higher energy densities and greater charge–discharge efficiencies than normal ferroelectrics for capacitive energy storage applications. Herein, dielectric energy storage behavior of several newly discovered relaxor ferroelectric polymers is studied from a molecular perspective. It is observed that the homopolymers exhibit very slim polarization–electric field loops and the highest charge–discharge efficiencies among ferroelectric polymers, which are attributed to the highly disordered chain conformation as evidenced from the scanning probe microscopy results. Based on the findings on the relaxor homopolymers, the benchmark relaxor ferroelectric terpolymers is revisited and insights into their outstanding capacitive performance are provided. Moreover, it is found that the disordered chain conformation in relaxor ferroelectric polymers remains as the ground state at varied temperatures and applied electric fields, which is in stark contrast to relaxor perovskites whose ground state is strongly dependent on temperatures and external electric fields. The discovery of the absence of thermal‐ and field‐induced phase transition in relaxor ferroelectric polymers makes this class of ferroelectric materials more attractive for advanced electronic and energy applications.