Applications of polymeric materials in electrical engineering increasingly require improvements in operating voltages, performance, reliability, and size reduction. However, the resulting increase on the electric field in electrical systems can prevent achieving these goals. Polymer composites, functionalized with conductive or semiconductive particles, can allow us to reduce the electric field, thus grading the field within the system. In this paper, a comprehensive review of field-grading materials, their properties, and recent developments and applications is provided to realize high-performance high-voltage engineering applications.