<p>Achieving high electrical performance in polymer composites typically requires high filler loadings, which increases materials costs, complicates processability, and compromises both flexibility and recyclability. Here, chemically recyclable poly(disulfide)@Ti₃C₂T_x MXene composites with an exceptionally low percolation threshold are developed via electrostatic self-assembly and compression molding. A segregated network is formed by assembling negatively charged Ti₃C₂T_x MXene nanosheets onto positively charged poly(disulfide) particles, facilitating the formation of continuous conductive pathways at interparticle interfaces. This architecture enables an ultralow percolation threshold of 0.063 vol%, electrical conductivity up to 1.78 × 10³ S m^− 1, and absorption-dominated electromagnetic interference (EMI) shielding effectiveness of 83.9 dB at 3.8 vol% MXene. The segregated structure also enhances the mechanical properties of the composites including modulus, strength, and toughness. Furthermore, the poly(disulfide) matrix, composed of five-membered cyclic disulfide monomers, undergoes complete depolymerization under mild catalytic conditions, allowing for chemical recycling of monomers, crosslinkers and MXene fillers. This approach offers a generalized pathway toward high-performance, sustainable EMI shielding materials with tunable electrical, mechanical properties, and recyclability.</p> Graphical Abstract <p></p>