The electrocaloric effect (ECE) in dielectric materials has great potential in realizing solid-state cooling devices with compact size and high efficiency, which are highly desirable for a broad range of applications. This paper presents the general considerations for dielectric materials to achieve large ECE and reviews the experimental efforts investigating ECE in various polar dielectrics. For practical cooling devices, an ECE material must possess a large isothermal entropy change besides a large adiabatic temperature change. We show that polar dielectrics operated at temperatures near order–disorder transition have potential to achieve large ECE due to the possibility of large change in polarization induced by electric field and large entropy change associated with the polarization change. We further show that indeed the ferroelectric poly(vinylidene fluoride–trifluoroethylene)-based polymers display a large ECE, i.e., an isothermal entropy change of more than 55 J (kgK)−1 and an adiabatic temperature change of more than 12 °C, at temperatures above the order–disorder transition.