The isomerization process of glyoxylic acid (GA) conformers and their complexes with a water molecule were studied in a low temperature argon matrix. The research target was to understand how starting conformation and complexation affects the near-IR (NIR) induced conformer interconversion. The most stable GA conformer (Tc) is characterized by an intramolecular hydrogen bond, and it is found to undergo light-induced conformer interconversion slower than the open (Tt) conformer. Upon complexation with water, the isomerization processes slow down in the case of the Tc conformer, whereas for the Tt-based complex the influence of water is negligible on the isomerization process.