In situ electrical conductivity and X‐ray tomography experiments are conducted on a conductive polymer composite containing polyvinylidene fluoride (PVDF) copolymer, copper (Cu), and tin (Sn) during thermal annealing. During annealing, the electrical resistivity drops by an order of magnitude, while X‐ray tomography, electron microscopy, and spectroscopy results show increasingly homogeneous dispersion of Sn in the conductive filler network, accompanied by the formation of Cu–Sn intermetallic around Cu and Sn particles. This study provides detailed insight into the morphological origins of the beneficial effect of thermal annealing on the electrical properties of conductive composites containing low melting metal fillers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45399.