Poly(L-lactic acid) (PLA) is a biodegradable fiber, and a promising material for use in biomedical applications. However, its hydrophobicity, low hydrolyzability, and poor cell adhesion can be problematic in some cases; consequently, the development of improved PLA-based materials is required. In this study, chitosan-coated (CS-coated) PLA was prepared by plasma treatment and the layer-by-layer (LBL) method. Plasma treatment prior to CS coating effectively hydrophilized and activated the PLA surface. The LBL method was used to increase the number of CS and sodium alginate (SA) coating layers by electrostatically superposing alternating anionic and cationic polymers. The prepared fibers were characterized by tensile testing, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), nitrogen analysis and degradation testing, which revealed that the 100 W plasma treatment for 60 s was optimum, and that plasma treatment and the LBL method effectively coated CS onto the PLA fibers. The existence or not of a coating on the PLA fiber did not appear to influence the degradation of the fiber, which is ascribable to the extremely thin coating, as evidenced by nitrogen analysis and SEM. The CS-coated PLA fibers were prepared without damaging the PLA surface and can be used in biomaterial applications such as suture threads.