The UV–VIS and the acid–base behaviour of three aminophenol ligands (m-aminophenol, 4-amino-2-hydroxytoluene, 2-amino-5-ethylphenol) was studied by spectrophotometry at t=25°C and I=0.004mol L −1 in aqueous solution. The stability constants for their Zn 2+ complexes were determined and compared by potentiometry at I=0.1mol L −1 in NaCl and UV–VIS spectrophotometry at I=0.004mol L −1 . The results showed, in the pH range between 2 and 7, a very weak complexing ability towards the Zn 2+ ion for all aminophenols under study. For all the systems, at higher pHs, the strongest species are ML(OH) 2 − and especially M 2 L(OH) 3 0 . Stability constant values show that the interactions between Zn 2+ and aminophenols under study are rather weak. For example, regarding the formation equilibrium M(OH) 2 0 +L − =ML(OH) 2 − , we found logK=4.6, 4.3 and 4.8, for m-aminophenol, 4-amino-2-hydroxytoluene, 2-amino-5-ethylphenol, respectively, at t=25°C and I=0.1mol L −1 in NaCl. Speciation profiles for all the systems were also calculated. In this investigation the spectrophotometric technique was used as a validating method of the speciation model calculated on the basis of potentiometric evidence and also to obtain reliable formation constant values. Suggested values, obtained by taking into account the results of both the techniques, were calculated at I=0, 0.1mol L −1 and t=25°C.