Polyvinylidene fluoride (PVDF) is a versatile electroactive polymer with broad applications in electronics, energy, and biological fields. Unique dielectric property is one of the many reasons for its popularity in these applications, and it brings up both opportunities and challenges. This study aimed at a better understanding of conductivity relaxation, one of the major relaxation mechanisms found in PVDF materials at elevated temperatures, indicating a transition of short-range conduction to long range conduction. Conductivity relaxation is critical to both high temperature dielectric properties and transport behaviors of PVDF based functional materials. However, it is insufficiently understood, in comparison to other relaxation processes in PVDF. Our previous study suggested that, unlike other relaxation mechanisms, conductivity relaxation exhibited high sensitivity to processing and testing parameters. As a part of the effort to gain in-depth understanding of conductivity relaxation, this study explored the effects of temperature and thermal history on the conductivity relaxation in the PVDF compression molded at 200oC. The preliminary results revealed the coupling of conductivity relaxation with Maxwell-Wagner-Sillars (MWS) relaxation, as temperature increased to melting temperature of PVDF. Decoupled conductivity relaxation and MWS relaxation were not observed in the PVDF specimens after full annealing treatment. This might suggest that the conductivity relaxation was related to the defects in the underdeveloped crystal structures which were largely eliminated in melting and full annealing processes used in this study. Such findings also showed negligible dependence on the molecular weight of PVDF and thickness of testing