Polymer-based conductive adhesives (PbCAs) have emerged as key materials for electromagnetic wave interference (EMI) protection. They are increasingly replacing traditional metals due to their environmental friendliness, low-temperature processing, and flexibility. This review systematically elaborates on the conductive mechanisms of PbCAs, which are dominated by percolation theory and quantum tunneling effects. Furthermore, recent advances in the encapsulation of PbCAs within polymer matrices (e.g., epoxy, polyurethane) and/or with conductive fillers (e.g., metals, carbon-based materials, MXenes) have been highlighted. These innovations facilitate their expanded applications in EMI protection, including both EMI shielding and electromagnetic wave absorption. Despite significant advancements, challenges persist in balancing high conductivity with favorable mechanical properties and long-term stability under harsh service conditions. Future development is expected to focus on fillers with a low percolation threshold, optimized structural designs, and multifunctional applications in flexible and wearable electronics. These advancements aim to meet the requirements of miniaturized, high-performance electronic devices.