Glycerol is UV/vis spectroscopically characterized by using suitable solvatochromic polarity probes spanning a wide temperature range of 353 to 77 K. For the first time we find experimental evidence that, when the solvent preserves its internal structure in a broad range of temperatures, all solvatochromically derived solvent parameters (i.e., SP, SdP, SA, and SB) also maintain their values unchanged. On the basis of these solvatochromic measurements, it is shown that, below 180 K, glycerol efficiently blocks the molecular structure of conformationally flexible solutes.