An optical single-molecule study is reported of a quickly frozen solution of 2.3,8.9-dibenzanthanthrene (DBATT) in n-tetradecane at 1.4 K. The orientation has been measured of several hundreds of DBATT molecules within a confocal detection volume of similar to 10 mum(3) as a function of their resonance frequency in the range of the two 0-0 bands in the fluorescence-excitation spectrum. Each band is found to correspond to a distinct distribution of orientations of DBATT molecules. A particular resonance frequency within a band is not correlated with a specific molecular orientation.