The branching structures in natural rubber (NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the complexity of the system. Herein, polyisoprene-(polyisoprene-g-polylactide) (PI-PLA) as model compound containing branching structure was designed and synthesized, which can improve the modulus, strength and viscoelasticity activation energy compared to those of the pristine polyisoprene (PI). The reason is that the branching structure contributes to the entanglement between polyisoprene chains. In order to probe the effect of branching structure on noncovalently crosslinked system, the polyisoprene block of PI-PLA was epoxidized and mixed with Fe3+ ions to introduce coordination bonds. Compared with the linear counterpart, the branching structure obviously enhanced activation energy of coordinated polyisoprenes, remarkably improving the mechanical properies of elastomer.