This study was aimed at preparing electromagnetic interference (EMI) shielding materials based on carbon black (CB), carbon fiber (CF), bamboo charcoal (BC), and epoxy resin. The effects of adding bamboo charcoal on the mechanical properties and electrical resistivity of epoxy composites were studied. Scanning electron microscopic (SEM) analysis, electrical resistivity, and electromagnetic interference (EMI) shielding effectiveness were also investigated. The composites were prepared at 120 °C by the curing-molding method through blending the fillers in epoxy resin. The results revealed that the BC/CB and BC/CF composites had perfect conductive network structure and resulted in better dynamic thermal mechanical properties. The electrical resistivity declined with the increase of bamboo charcoal contents; consequently, the EMI shielding effectiveness improved gradually. The lowest electrical resistivity, down to 0.071 Ω·m, corresponded to the best EMI shielding effectiveness of BC/CF composites, which could be above 60 dB over a frequency range of 30 MHz to 1500 MHz while the carbon fiber content was at 40 wt.%.