Abstract Due to the shortage of petroleum resources, poly(lactic acid) (PLA), a biodegradable polymer, has been widely considered as a replacement for traditional petroleum-based polymers. Therefore, multifunctional PLA composites have become increasingly popular. In this study, conductive carbon nanotubes (CNTs) and magnetic nano-Fe3O4 fillers were melt-blended with PLA. The impact of CNTs and nano-Fe3O4 composition on the electrical and electromagnetic interference (EMI) shielding properties of PLA nanocomposites was investigated in detail by adjusting the CNTs-to-nano-Fe3O4 ratio. When the hybrid filler content was fixed at 10 wt%, the electrical conductivity results indicated that the addition of single CNTs could effectively improve the conductivity of the nanocomposites, while nano-Fe3O4 contribution was hardly noted. A suitable ratio of electromagnetic hybrid fillers can yield excellent synergistic effects in EMI shielding properties. The nanocomposites containing CNTs and nano-Fe3O4 in a 50:50 ratio exhibited excellent electrical conductivity (90.6 S·m−1) and EMI shielding effectiveness (EMI SE ∼ 40.5 dB). This is primarily because CNTs provide good electrical conductivity, but the addition of magnetic nano-Fe3O4 provides additional interfacial polarization and eddy current losses caused by its dielectric and magnetic properties. These properties synergistically result in an impedance mismatch, dielectric loss, and polarization relaxation of the composite materials, improving the shielding properties against electromagnetic waves. Further, it was found that changing the ratio of electromagnetic hybrid fillers also affected electromagnetic wave absorption. When the ratio of CNT-to-nano-Fe3O4 was 25:75, the nanocomposites had an EMI SE of 24.6 dB, and the absorptivity could reach the maximum (40.3%). Thus, this study provides a valuable reference for preparing multifunctional polymer nanocomposites by constructing electromagnetic hybrid filler networks.