The discovery of nanodipolar π -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 π -conjugated oligomer-containing polymers for the development of high energy density capacitor materials.

High‐performance nanodielectric materials are built by C. Tang and co‐workers based on nano‐dipolar π‐conjugated oligomer thiophenecontaining polymers that exhibit high permittivity and low dielectric loss over a wide range of frequencies (100 Hz to about 10 MHz). Highly polarizable and fast‐responsive nano‐dipoles from nanoscale crystalline domains from π–π stacked oligomer thiophenes are believed to dictate the performance. These materials could be used to construct high energy‐density capacitors. The cover image is courtesy of Xiaodong Yin and Mitra Ganewatta.