Shape memory structures are playing an important role in many cutting-edge intelligent fields. However, the existing technologies can only realize 4D printing of a single polymer or metal, which limits practical applications. Here, we report a construction strategy for TSMP/M heterointerface, which uses Pd2+-containing shape memory polymer (AP-SMR) to induce electroless plating reaction and relies on molecular dynamics, which has both shape memory properties and metal activity and information processing power. Through multi-material DLP 3D printing technology, the interface can be 3D selectively programmed on functional substrate parts of arbitrary shapes to become 4D electronic smart devices (Robotics). Microscopically, this type of interface appears as a composite structure with a nanometer-micrometer interface height, which is composed of a pure substrate layer (smart materials), an intermediate layer (a composite structure in which metal particles are embedded in a polymer cross-linked network) and a pure metal layer. The structure programmed by TSMP/M heterointerface exhibits both SMA characteristics and metal properties, thus having more intelligent functions (electroactive, electrothermal deformation, electronically controlled denaturation) and higher performance (selectivity of shape memory structures can be realized control, remote control, inline control and low voltage control). This is expected to provide a more flexible manufacturing process as platform technology for designing, manufacturing and applying smart devices with new concepts, and promote the development of cutting-edge industries such as smart robots and smart electronics.