The bulk carbon materials were prepared via solidification, molding and pyrolysis using thermosetting phenolic resin as raw materials. The effects of pyrolysis temperature and FeCl3 catalyst on micro morphology, ordering degree and electromagnetic interference shielding effectiveness (EMI SE) in X-band of phenolic resin pyrolytic products were investigated through X-ray diffraction, TG-DSC, laser Raman spectroscopy and scanning electron microscopy. The results show that the final pyrolytic products of phenolic resin were amorphous carbon. The TG-DSC results indicate that the carbon yield of the phenolic resin pyrolyzing at 1000℃ was 55%. The ordering degree and the conductivity of phenolic resin pyrolytic products increased with pyrolysis temperature rising, and the EMI SE first increased then decreased. The EMI SE of sample pyrolyzing at 900℃ was 28.2dB. Large amounts of in-situ multi-walled carbon nanotubes grew and formed the conductive network in the phenolic resin pyrolyzing at 1000℃ with 0.5wt% FeCl3. These led to a high EMI SE. The EMI SE of phenolic resin significantly increased pyrolyzing at 1500℃ with 0.5wt% FeCl3, especially in low frequency.