The general utilization of fluorescence for pharmaceutical analysis is discussed and the native fluorescence of several barbiturates and the characteristics of each are reported. Concentration ranges applicable for linear response with the instrumentation used are also discussed. Utilization of direct measurement of the fluorescence of barbiturates for quantitative analysis provides simple, and thus faster, analysis with relatively the same accuracy and precision as conventional spectrophoto-metric methods. The wavelengths observed for emission and excitation make most analyses applicable to filter instrumentation. The simplicity of the analysis makes it generally applicable for automation.