In this work, solution blending was used to prepare series of polyvinylidene fluoride (PVDF)/graphene nanoplatelet (GNP) nanocomposites to investigate the effect of GNP content on the formation of filler network structure. Thermorheological complexity was observed with increasing GNP content, which was substantiated by morphological observation. Three classical thermal conduction models were adopted and compared with the measured thermal conductivity as a function of GNP loading, among which the Agari model presented the most reasonable prediction. A four‐parameter model was proposed to reflect the cooling behaviors of the PVDF/GNP composites with the aid of an in‐situ temperature measurement, suggesting the formation of GNP network structure in the composites. The incorporation of GNP showed an obvious nucleating effect on the crystallization of PVDF without altering its crystal form. Owing to the competition between spatial effect and heterogeneous nucleation, both crystallization rate and enthalpy achieved the maximum values when 6% GNP was added.