Electromagnetic interference (EMI) shielding materials made of Ni-Co coated on web-like biocarbon nanofibers were successfully prepared by electroless plating. Biocarbon nanofibers (CF) with a novel web-like structure comprised of entangled and interconnected carbon nanoribbons were obtained using bacterial cellulose pyrolyzed at 1200°C. Paraffin wax matrix composites filled with different loadings (10, 20, and 30 wt%, resp.) of CF and Ni-Co coated CF (NCCF) were prepared. The electrical conductivities and electromagnetic parameters of the composites were investigated by the four-probe method and vector network analysis. From these results, the EMI shielding efficiencies (SE) of NCCF composites were shown to be significantly higher than that of CF at the same mass fraction. The paraffin wax composites containing 30 wt% NCCF showed the highest EMI SE of 41.2 dB (99.99% attenuation), which are attributed to the higher electrical conductivity and permittivity of the NCCF composites than the CF composites. Additionally, EMI SE increased with an increase in CF and NCCF loading and the absorption was determined to be the primary factor governing EMI shielding. This study conclusively reveals that NCCF composites have potential applications as EMI shielding materials.