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The enhancement of the electromagnetic interference shielding efficiency (EMI SE) for conductive polymer composites (CPCs) has garnered increasing attention. The shielding performance is influenced by conductivity, which is dependent on the establishment of effective conductive pathways. In this review, Schelkunoff’s theory on outlining the mechanism of electromagnetic interference shielding was briefly described. Based on the mechanism, factors that influenced the electrical percolation threshold of CPCs were presented and three main kinds of efficient methods were discussed for establishing conductive pathways. Furthermore, examples were explored that highlighted the critical importance of such conductive pathways in attaining optimal shielding performance. Finally, we outlined the prospects for the future direction for advancing CPCs towards a balance of enhanced EMI SE and cost–performance.