The persistent organic radical 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) protects its NO radical center by four methyl groups. Two of them are arranged tightly (t) on one side of the six-membered puckered heterocycle, and the other two more openly (o) on the other side. It is shown by OH stretching infrared spectroscopy in heated supersonic jet expansions that the hydrogen bond and aromatic ring of a first solvating benzyl alcohol have almost no preference for either side. An increased preference for the t side develops in