The electrical and dielectric response upon thermal expansion and contraction of polymer composites have been studied for thermoset polymers containing ceramic or metallic fillers. Before curing, the resistivity p of epoxy containing a metallic filler is in the range of 106 to 107 Ωcm. During curing a sudden reduction of p by eight orders of magnitude is observed. The shrinkage of the polymer during cross-linking and the build-up of internal stresses results in a lower interparticle contact resistance. The contraction can be reversed by heating. Around curing temperature, the resistivity increases by six to eight orders of magnitude due to the expansion of the material. The resistivity increases progressively until the percolation network of the conducting particles is interrupted and the composite reaches a high-ohmic state. Surprisingly, the critical temperature is related to the curing temperature and not to the glass transition temperature, as would be generally expected. Changes of the interparticle gap size can also be observed in the dielectric constant ε. For conducting fillers covered by a thin oxide layer, ε decreases by several orders of magnitude after a certain expansion has been achieved. However, for poorly conducting or insulating fillers dielectric response becomes insensitive to the gap distance. Hence, the electrical or dielectric response of polymers containing metallic fillers can be used as a sensitive probe for the internal stress state and the corresponding micro-structure of the composite.