The integrated circuits industry has been continuously producing microelectronic components with ever higher integration level, packaging density, and power density, which demand more stringent requirements for heat dissipation. Electronic packaging materials are used to pack these microelectronic components together, help to dissipate heat, redistribute stresses, and protect the whole system from the environment. They serve an important role in ensuring the performance and reliability of the electronic devices. Among various packaging materials, epoxy‐based underfills are often employed in flip‐chip packaging. However, widely used capillary underfill materials suffer from their low thermal conductivity, unable to meet the growing heat dissipation required of next‐generation IC chips with much higher power density. Many strategies have been proposed to improve the thermal conductivity of epoxy, but its application as underfill materials with complex performance requirements is still difficult. In fact, optimizing the combined thermal–electrical–mechanical–processing properties of underfill materials for flip‐chip packaging remains a great challenge. Herein, state‐of‐the‐art advances that have been made to satisfy the key requirements of capillary underfill materials are reviewed. Based on these studies, the perspectives for designing high‐performance underfill materials with novel microstructures in electronic packaging for high‐power density electronic devices are provided.