An eco-friendly strategy for the modification of polylactic acid (PLA) surface properties, using a solvent-free process, is reported. Reactive extrusion (REX) allowed the formation of new covalent bonds between functional molecules and the PLA polymeric matrix, enhancing its mechanical properties and modifying surface hydrophobicity. To this end, the PLA backbone was modified using two alkoxysilanes, phenyltriethoxysilane and N-octyltriethoxysilane. The reactive extrusion process was carried out under mild conditions, using melting temperatures between 150 and 180 °C, 300 rpm as screw speed, and a feeding rate of 3 kg·h−1. To complete the study, flat tapes of neat and functionalized PLA were obtained through monofilament melt extrusion to quantify the enhancement of mechanical properties and hydrophobicity. The results verified that PLA modified with 3 wt% of N-octyltriethoxysilane improves mechanical and thermal properties, reaching Young’s modulus values of 4.8 GPa, and PLA hydrophobic behavior, with values of water contact angle shifting from 68.6° to 82.2°.