AbstractStrong, conductive, and flexible materials with improving ion accessibility have attracted significant attention in electromagnetic interference (EMI) and foldable wearable electronics. However, it still remains a great challenge to realize high performance at the same time for both properties. Herein, a microscale structural design combined with nanostructures strategy to fabricate TOCNF(F)/Ti3C2Tx(M)@AgNW(A) composite films via a facile vacuum filtration process followed by hot pressing (TOCNF = TEMPO‐oxidized cellulose nanofibrils, NW = nanowires) is described. The comparison reveals that different microscale structures can significantly influence the properties of thin films, especially their electrochemical properties. Impressively, the ultrathin MA/F/MA film with enhanced layer in the middle exhibits an excellent tensile strength of 107.9 MPa, an outstanding electrical conductivity of 8.4 × 106 S m−1, and a high SSE/t of 26 014.52 dB cm2 g−1. The assembled asymmetric MA/F/MA//TOCNF@CNT (carbon nanotubes) supercapacitor leads to a significantly high areal energy density of 49.08 µWh cm−2 at a power density of 777.26 µW cm−2. This study proposes an effective strategy to circumvent the trade‐off between EMI performance and electrochemical properties, providing an inspiration for the fabrication of multifunctional films for a wide variety of applications in aerospace, national defense, precision instruments, and next‐generation electronics.