Abstract Conductive polymer composites (CPCs) that contain a segregated structure have attracted significant attentions because of their promising for fulfilling low filler contents with high electromagnetic interference (EMI) properties. In the present study, segregated poly(vinylidene fluoride) (PVDF)/multi-walled carbon nanotubes (MWCNTs) composites were successfully prepared by mechanical mixing and hot compaction. The PVDF/MWCNTs samples with 7 wt% filler content possess high electrical conductivities and high EMI shielding effectiveness (SE), reaching 0.06 S cm −1 and 30.89 dB (in the X-band frequency region), much higher than lots of reported results for CNT-based composites. And the EMI SE greatly increased across the frequency range as the sample thickness was improved from 0.6 to 3.0 mm. The EMI shielding mechanisms were also investigated and the results demonstrated absorption dominating shielding mechanism in this segregated material. This effective preparation method is simple, low-cost, and environmentally-friendly and has potential industrial applications in the future.