The proton magnetic resonance spectra of tetraamminecobalt(III) complexes with a series of amino alcohols have been analysed and the coupling constant data utilized to calculate the conformational populations for the various complexes. When substitution occurred at the carbon adjacent to the amine group, the equatorial orientation of the substituent was not markedly preferred over the axial. However, when substitution occurred adjacent to the alcohol group, the substituent was found to be exclusively in the equatorial orientation.