With the rapid development of society, polymer materials are widely used in automotive, construction, and electronic components due to their excellent properties such as easy processing, cheap price, and corrosion resistance. However, most polymers, such as rubber and leather, suffer from poor mechanical properties, susceptibility to micro cracking and ammability. In this paper, an epoxidized natural rubber (ENR)/polylactic acid (PLA)/chitosan (CS)/guanidine phosphate (GP) composite with certain self-healing and ame-retardant properties was successfully prepared. The network structure is constructed by forming thermoplastic elastomers (TVPs) through ENR and PLA, and the amino groups on CS and GP can form hydrogen bonds with ENR. which improves the mechanical properties of ENR/PLA composites and gives the ENR/PLA/CS/GP composites excellent self-healing properties. Secondly, CS and GP can also form intumescent ame retardants to improve the ame-retardant properties of ENR/PLA composites. Among them, the ENR/PLA/CS 2 /GP 4 composite can achieve 78% self-healing effect and 35.8% reduction in ame retardant heat release rate (HRR).