UV curing was introduced via a chemical treatment by adding small amounts of a hexafunctional acrylic monomer and a photoinitiator to improve the mechanical properties of PLA. This study also employed a semi-interpenetrated structured polymer network through the process of UV-curing. The UV curing behaviors were investigated using FTIR-ATR spectroscopy and gel fraction determination. Also, the tensile strength was investigated with different hexafunctional acrylic monomer contents and UV doses. The results showed that the crosslinking of UV-induced chemically treated PLA started at a low content of hexafunctional acrylic monomer, resulting in a significant improvement of the mechanical properties compared to those of neat PLA due to crosslinking.