During radio frequency (RF) thawing—tempering (defrosting) of frozen food products, some regions, mostly along the corners and edges, heat—thaw first due to the strong interaction of electric field and evolved heating leading to temperature increase. Resulting higher power absorption along these regions, compared to the rest of the volume, is the major cause of this problem. Besides, increase in temperature with phase change results in a significant increase of dielectric properties. This situation leads to runaway heating, which triggers the non-uniform temperature distribution in an accelerated manner. All these power absorption and temperature non-uniformity-based changes lead to significant quality changes, drip losses, and microbial growth. Based on this background, the objective of this review was to provide a comprehensive background regarding the most relevant and novel defrosting application studies using RF process, dielectric property data for frozen foods in the RF band, and novel mathematical modeling based computer simulation approaches to achieve a uniform process. Experimental and modeling studies were related with electrode position, sample geometry and size, electrode gap of the applied RF process, and the potential of charged electrode. Applying translational and rotational movement of the food product and the charged electrode vertical movement during the process to adjust the electric field and use of two-cavity systems and curved electrodes were also explained in detail. The data presented in this review is expected to give an insight information for further development of innovative RF thawing/tempering systems.