Polyamide66 (PA66) hydrolysis affects the mechanical properties of Polyamide66/glass fiber (PA66/GF) composites. We investigated the effects of monoethylene glycol (MEG) on the degree of hydrolysis and mechanical properties of four different commercial PA66/glass fiber composites. Using pyrolysis-gas chromatography/mass spectrometry (py-GC/MS), we identified the byproducts of PA66 composite hydrolysis: carboxylic acid and alkylamine substances. The degree of hydrolysis increased as the immersion time in MEG increased. However, the tensile and flexural properties decreased due to hydrolysis. The tensile strength decreased by 42–45%; however, elongation increased by 23–63%. When PA66 absorbs MEG at 130 °C, the materials molecular chains’ bonding force decreased, resulting in increased elongation.