The growing use of explosives by terrorists and criminals creates a need for instrumentation which can rapidly analyze these energetic compounds, preferably on site. Direct analysis in real time (DART) is a promising technology for surface analysis with little or no sample preparation. Therefore, DART ionization is evaluated for use in detecting explosives on solid substrates and in liquid matrices. Fifteen explosives were chosen as a consequence of their common usage. Five surfaces were chosen to represent a wide range of physical properties such as composition, porosity, surface morphology, and thermal and electrical conductivity. Additionally these surfaces are commonly found in everyday surroundings. All 75 compound-surface combinations produced a clear, easily identifiable, mass spectra characteristic of the targeted analyte. Simultaneous detection of five explosives is demonstrated on these same surfaces. Lastly, rapid detection of trace contamination in common fluids is also explored.