The discovery of nanodipolar pi-conjugated oligomer-containing polymers as high performance nanodielectric materials with high permittivity and low dielectric loss over a wide range of frequency (100 Hz-4 MHz) is reported. Terthiophene-containing methacrylate polymers are synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Both X-ray and thermal studies indicate the formation of small crystalline domains of terthiophene side chains dispersed in amorphous matrix. The highly polarizable and fast-responsive nanodipoles from the nanoscale crystalline domains (<2 nm) are believed to dictate the performance. These polymers uniquely satisfy nanodipole architectures conjectured two decades ago to guide the design of high performance nanodielectric materials. This unprecedented approach can be generalized to a variety of pi-conjugated oligomer-containing polymers for the development of high energy density capacitor materials.