In this work, the surface of I-Ti3C2Tx MXene was modified by (MgAl-)LDH via coprecipitation followed by the introduction of BTA, forming the novel I-Ti3C2Tx@LDH/BTA (ITLB) heterostructure nanocomposites. ITLB acted as a pH-responsive nanocontainer to release benzotriazole (BTA) and adsorbed/captured Cl- ions by ion exchange. ITLB could be systematically arranged within an epoxy matrix, enhancing interface interaction and improving mechanical properties. The ITLB/EP coating exhibited excellent corrosion protection and self-healing performance. The impedance value of the intact ITLB/EP coating was 1011 Ω⋅cm2, which was three orders of magnitude higher than that of EP, and presented the highest Rc and Rct values compared to other coatings throughout the immersion period. When defects in the ITLB/EP coating, ITLB underwent a rapid pH-response to localized corrosion to release BTA, forming a dense protective [BTA-Fe-BTA]n complex with Fe2+ and effectively preventing further corrosion. Thus, ITLB exhibited dual functionality as a nanocomposite corrosion inhibitor, providing both pH-response behavior and intelligent protection. This newly created 2D/2D heterostructure nanocomposite will provide the theoretical basis and technical support for the development of intelligent coatings.