Silicon Anode is considered a most critical component for advanced lithium battery since it has about 10 folds higher theoretical capacity than that of conventional graphite anode. However, Si suffers from huge volume change during lithiation/ delithiation process has led to pulverization and the formation of unstable SEI layer with the electrolyte that quickly deteriorated the cyclic performance of lithium battery. In this study, smart polymer material bearing breathable network-like structure is employed to encapsulate the high energy anode material through photo polymerization. The monomers of the smart polymer in the solvent are adsorbed first to the surface of silicon particle, followed by photo-polymerization to form the dendrimer network-like structure which homogeneously encapsulated the active anode. During charging and discharging process, the flexible and breathable protection layer effectively retained the pulverized anode materials due to the huge volume change, and avoided a direct contact with the liquid electrolyte. Both functions are essential to inhibit the dissolution of active material and responsible for maintaining the cyclic performance of Si anode battery. NMR spectroscopy is used to follow the photo-polymerization identified, and the effect of the coating and the change of morphology after extensive charge and discharge cycle are identified by SEM and TEM. Current results show the coating of a network-like breathable polymer protection layer is effective in preserving the integrity and the structure of Si anode, leading to improved life cycle performance.