Abstract Thin-layer chromatography (TLC) of some 2-alkyl-, 2-aryl- and 2,2′-bis-benzothiazoles has been examined to develop analytical procedures and to determine the influence of substituents. No simple relationship was found for the R M values of the 2-alkyl derivatives but the R M values of the 2,2′-bis compounds showed linear behaviour, indicative of mixed partition-absorption and pure partition separation, respectively. Δ R M values were calculated for the compounds and shown to be characteristic of structural features. Gas-liquid chromatographic (GLC) behaviour was studied on SE-30 and Carbowax 20M columns. In this case both 2-alkyl- and 2,2′-bis-benzothiazoles show exponential relationships between retention times and carbon chain length of substituents. The calculated TLC and GLC relationships can provide a basis for the identification of components of reaction mixtures of benzothiazoles.