This study investigated the effect of hemp fiber pretreatments (water and sodium hydroxide) combined with silane treatment, first on the fiber properties (microscale) and then on polylactide (PLA) composite properties (macroscale). At the microscale, Fourier transform infrared, thermogravimetric analysis, and scanning electron microscopy investigations highlighted structural alterations in the fibers, with the removal of targeted components and rearrangement in the cell wall. These structural changes influenced unitary fiber properties. At the macroscale, both pretreatments increased the composites’ tensile properties, despite their negative impact on fiber performance. Additionally, silane treatment improved composite performance thanks to higher performance of the fibers themselves and improved fiber compatibility with the PLA matrix brought on by the silane couplings. PLA composites reinforced by 30 wt.% alkali and silane treated hemp fibers exhibited the highest tensile strength (62 MPa), flexural strength (113 MPa), and Young’s modulus (7.6 GPa). Overall, the paper demonstrates the applicability of locally grown, frost-retted hemp fibers for the development of bio-based composites with low density (1.13 to 1.23 g cm−3).