Materials that have high dielectric constants, high energy densities and minimum dielectric losses are highly desirable for use in capacitor devices. In this sense, polymers and polymer blends have several advantages over inorganic and composite materials, such as their flexibilities, high breakdown strengths, and low dielectric losses. Moreover, the dielectric performance of a polymer depends strongly on its electronic, atomic, dipolar, ionic, and interfacial polarizations. For these reasons, chemical modification and the introduction of specific functional groups (e.g., F, CN and R−S(=O)₂−R´) would improve the dielectric properties, e.g., by varying the dipolar polarization. These functional groups have been demonstrated to have large dipole moments. In this way, a high orientational polarization in the polymer can be achieved. However, the decrease in the polarization due to dielectric dissipation and the frequency dependency of the polarization are challenging tasks to date. Polymers with high glass transition temperatures (T_g) that contain permanent dipoles can help to reduce dielectric losses due to conduction phenomena related to ionic mechanisms. Additionally, sub-Tg transitions (e.g., γ and β relaxations) attributed to the free rotational motions of the dipolar entities would increase the polarization of the material, resulting in polymers with high dielectric constants and, hopefully, dielectric losses that are as low as possible. Thus, polymer materials with high glass transition temperatures and considerable contributions from the dipolar polarization mechanisms of sub-T_g transitions are known as “dipolar glass polymers”. Considering this, the main aspects of this combined strategy and the future prospects of these types of material were discussed.