Evaluation of the analytical utility of selected excited state properties of molecules for chemical analysis was performed. The effects of molecular structure and microenvironment on the singlet excited state properties of an atabrine-based homologous series and the parent compound were determined. The ultraviolet and visible spectra, the fluorescence spectra, fluorescence lifetime, and quantum yields were determined. These quantities were examined in different polarity solvents and for both the acid and the base forms of the molecular species. These excited state properties are used to illustrate what molecular properties permit differentiation between similar species. By selecting certain solution conditions, it may be possible to improve the sensitivity and selectivity of fluorescence analysis through use of the variations in fluorescence lifetimes and quantum yields.