MoS2 is an additive used to improve the tribological properties of plastics. In this work, it was decided to verify the use of MoS2 as a modifier of the properties of PLA filaments used in the additive FDM/FFF technique. For this purpose, MoS2 was introduced into the PLA matrix at concentrations of 0.025–1.0% by weight. Through extrusion, a fibre with a diameter of 1.75 mm was obtained. 3D printed samples with three different filling patterns were subjected to comprehensive thermal (TG, DSC and HDT), mechanical (impact, bending and strength tests), tribological and physicochemical characteristics. The mechanical properties were determined for two different types of fillings, and samples with the third type of filling were used for tribological tests. Tensile strength has been significantly increased for all samples with longitudinal filling with improvement up to 49%. In terms of tribological properties, higher values of the addition (0.5%) caused a significant increase of up to 457% of the wear indicator. A significant improvement in processing properties in terms of rheology was obtained (416% compared to pure PLA with the addition of 1.0%), which translated into more efficient processing, increased interlayer adhesion and mechanical strength. As a result, the quality of printed objects has been improved. Microscopic analysis was also carried out, which confirmed the good dispersion of the modifier in the polymer matrix (SEM-EDS). Microscopic techniques (MO, SEM) allowed for the characterization of the effect of the additive on changes in the printing process (improvement of interlayer remelting) and to assess impact fractures. In the tribological area, the introduced modification did not bring spectacular effects.