Radio frequency (RF) heating is rapid, volumetric, and can penetrate most food packaging material. Thus, it is suited for in-packaged food pasteurization applications. However, the non-uniform heating problem needs to be resolved. In this study, a method of adding Polyetherimide (PEI) cylindrical blocks on top of and at the bottom of peanut butter samples in a cylindrical jar (d = 10 cm, h = 5 cm) was evaluated to improve RF heating uniformity. A computer simulation model built with COMSOL Multiphysics® was used for heating pattern prediction, and a new temperature uniformity index was proposed to suitably evaluate pasteurization process heating uniformity. Results showed that a pair of PEI blocks with a diameter of 8 cm among all five diameters (2, 4, 6, 8, and 10 cm) added to the cold spots of a given peanut butter sample could make the sample reach the best heating uniformity. Furthermore, the best height of PEI blocks with a diameter of 8 cm that allows the sample to be heated most uniformly was found to be 1.3 cm after sweeping from 0.1 to 2.3 cm with a step of 0.1 cm. Simulation results also showed that the combination of PEI surrounding and the addition of 8 cm diameter PEI blocks could further control the temperature distribution range in peanut butter within 7.1 °C when the peanut butter was heated from 23 to 70 °C. The newly developed temperature uniformity index provided a more reasonable evaluation on heating uniformity of pasteurization process than the traditional uniformity index.