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The spectral and dynamic properties of <i>2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)</i> in a series of <i>1-alkanols</i> ranging from <i>methanol</i> to <i>1-decanol</i> over a temperature range 100–300 K were investigated by <i>electron spin resonance (ESR</i>). The main characteristic ESR temperatures connected with slow to fast motion regime transition; <i>T</i>_50G ‘s and <i>T</i>_X1^fast ‘s are situated above the corresponding glass temperatures, <i>T</i>_g, and for the <i>shorter members,</i> the <i>T</i>_50G ‘s lie above or close to melting point, <i>T</i>_m, while the <i>longer ones</i> the <i>T</i>_50G < <i>T</i>_m relationship indicates that the <i>TEMPO molecules</i> are in the local disordered regions of the <i>crystalline media</i>. The <i>T</i>_50G ‘s and especially <i>T</i>_X1^fast ‘s are compared with the dynamic crossover temperatures, <i>T</i>_X^VISC = 8.72<i>M</i>^0.66, as obtained by fitting the viscosity data in the liquid <i>n-alkanols</i> with the empirical power law. In particular, for <i>N</i>_C > 6, the <i>T</i>_X1^fast ‘s lie rather close to the <i>T</i>_X^VISC resembling <i>apolar n-alkanes</i> [PCCP 2018,<i>20</i>,11145-11151], while for <i>N</i>_C < 6, they are situated in the vicinity of <i>T</i>_m. The absence of a coincidence for lower<i>1-alkanols</i> indicates that the <i>T</i>_50G is significantly influenced by the mutual interaction between the <i>polar TEMPO</i> and the <i>protic polar medium</i> due to the increased polarity and proticity destroyed by the larger-scale melting transition.