Engineering the Dielectric Constants of Polymers: From Molecular to Mesoscopic Scales

Abstract Polymers are essential components of modern‐day materials and are widely used in various fields. The dielectric constant, a key physical parameter, plays a fundamental role in the light‐, electricity‐, and magnetism‐related applications of polymers, such as dielectric and electrical insulation, battery and photovoltaic fabrication, sensing and electrical contact, and signal transmission and communication. Over the past few decades, numerous efforts have been devoted to engineering the intrinsic dielectric constant of polymers, particularly by tailoring the induced and orientational polarization modes and ferroelectric domain engineering. Investigations into these methods have guided the rational design and on‐demand preparation of polymers with desired dielectric constants. This review article exhaustively summarizes the dielectric constant engineering of polymers from molecular to mesoscopic scales, with emphasis on application‐driven design and on‐demand polymer synthesis rooted in polymer chemistry principles. Additionally, it explores the key polymer applications that can benefit from dielectric constant regulation and outlines the future prospects of this field.