The application of techniques to improve the surface finish of pieces obtained by fused deposition modelling, as well as other functional aspects, is of great interest nowadays. Polylactic acid, a biodegradable material, has been considered a possible substitute for petroleum-based polymers. In this work, different chemical post-processing methods are applied to polylactic acid pieces obtained by fused deposition modelling and some characteristics are studied. Structural, thermal, and crystallinity property changes are analyzed according to the treatments applied. This can prevent degradation, eliminate the glass transition phase of the material, and thereby increase the thermal resistance by about 50 °C. An improvement in the roughness of the pieces of up to 97% was also found.