Conductive particle-filled polymer composites are promising materials for applications where both the merits of polymer and conductivity are required. The electrical properties of such composites are controlled by the particle percolation network present in the polymeric matrix. In this study, the electrical properties of crosslinked carbon black–epoxy–amine (CB-EA) composites with various CB concentrations are studied at room temperature as a function of the AC frequency f. A transition at critical frequency fc from the DC plateau σDC to a frequency-dependent part was observed. Conductivity mechanisms for f > fc and f < fc were investigated. By considering the fractal nature, conduction for f > fc was verified to be intra-cluster charge diffusion. For f < fc, with the assistance of conductive atomic force microscopy (C-AFM), the conduction behavior of individual clusters can be observed, revealing both linear and nonlinear I–V characteristics. By combining microtoming and C-AFM measurements, 3D reconstructed images offer direct evidence that the percolating network of these materials consists of both a low-conductivity part, in which the charge transports through tunneling, and a high-conductivity part, which shows ohmic electrical properties. Nevertheless, for these CB-EA composites, the presence of these non-ohmic contacts still leads to Arrhenius-type behavior for the macroscopic conductivity.