Many biaryl compounds possess atropisomerism due to the steric hindrance of substituents at the ortho-position of the two aromatic moieties. Upon heating, atropisomers may have enough energy to surpass the rotational energy barrier and racemize. The thermal stability of five atropisomers was studied using chiral chromatography by following the change in enantiomeric excess ratio at different temperatures. The first order racemization reaction rate was obtained at a given temperature as the slope of the change in enantiomeric excess ratio versus time. For each atropisomer, the racemization rates at different temperatures led to the value of the rotational energy barrier for racemization, ΔG‡, and to the racemization half lifetime, t1/2, indicating the atropisomer thermal stability. Binaphthol started to racemize significantly at temperature of 190°C and above while binaphthyldiamine was much more stable showing little or very minor racemization up to 210°C. A chloro-substituted phenylamino-naphthol was very sensitive to thermal racemization starting at a low 40°C.