Special separation membranes are widely employed for separation and purification purposes under challenging operating conditions due to their low energy consumption, excellent solvent, and corrosion resistance. However, the development of membranes is limited by corrosion‐resistant polymer substrates and precise interfacial separation layers. Herein, polyaniline (PANI) is employed to achieve insitu anchoring of multiple interfaces, resulting in the fabrication of polyaniline@graphene oxide/polyether ether ketone (PANI@GO/PEEK) membranes. Insitu growth of PANI achieves the adequate bonding of the PEEK substrate and GO separation interface, which solves the problem of solution processing of PEEK and the instability of GO layers. By bottom‐up confined polymerization of aniline, it could control the pore size of the separation layer, correct defects, and anchor among polymer, nano‐separation layer, and nano‐sheet. The mechanism of membrane construction within the confined domain and micro‐nano structure modulation is further explored. The membranes demonstrate exceptional stability realizing over 90% rejection in 2 m HCl, NaOH, and high temperatures. Additionally, –membranes exhibit remarkable durability after 240 days immersion and 100 h long‐term operation, which display the methanol flux of 50.2 L m⁻² h⁻¹ and 92% rejection of AF (585 g mol⁻¹). This method substantially contributes to special separation membranes by offering a novel strategy.

Thermally reversible self-healing polymer (SHP) electrolyte membranes are obtained by Diels-Alder cycloaddition and electrolyte embedding. The SHP electrolytes membranes are found to display high ionic conductivity, suitable flexibility, remarkable mechanical properties and self-healing ability. The decomposition potential of the SHP electrolyte membrane is about 4.8 V (vs. Li/Li⁺) and it possesses excellent electrochemical stability, better than that of the commercial PE film which is only stable up to 4.5 V (vs. Li/Li⁺). TGA results show that the SHP electrolyte membrane is thermally stable up to 280 °C in a nitrogen atmosphere. When the SHP electrolyte membrane is used as a separator in a lithium-ion battery with an LCO-based cathode, the SHP membrane achieved excellent rate capability and stable cycling for over 100 cycles, and the specific discharge capacity could be almost fully recovered after self-healing. Furthermore, the electrolyte membrane exhibits excellent electrochemical performance, suggesting its potential for application in lithium-ion batteries as separator material.