Poly-lactic electrospun porous fibers have been widely used in tissue engineering scaffolds. However, the application of linear Poly-lactic is limited due to its poor hydrophilicity, which leads to phase separation and has been seldom used in porous fiber preparation. Instead, using of branching Poly-lactic acts as a new effective method to prepare porous fibers because it can increase Poly-lactic polar property and make it easy to be formulated in the following application. In current study, we prepared an ultra-high molecular weight of high branching Poly-lactic with glycerol as the initiator by controlling the ring-opening polymerization time, adding amount of catalyst and glycerol. The structure, molecular weight and thermal properties of copolymers were tested subsequently. The result showed that the surface of the high branching Poly-lactic films is smooth, hydrophilic and porous. This branching Poly-lactic formed electrospun porous fibers, possessed a strong adsorption of silver ion. Comparing with the application of linear Poly-lactic and 3-arm Poly-lactic materials, our study provided a simple and efficient way to synthesize branching Poly-lactic polymer and prepare electrospun porous fibers, which may provide potential applications in the field of biomaterials for tissue engineering or antibacterial dressing.