Mass analysis is demonstrated for the detection of sub-microgram quantities of explosive samples on a metallic surface at atmospheric pressure using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples for subsequent electrospray ionization and transfer into a time-of-flight mass spectrometer. LEMS was used to detect 2,3-dimethyl-2,3-dinitrobutane (DMNB), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), 3,4,8,9,12,13-hexaoxa-1,6-diazabicyclo[4.4.4]tetradecane (HMTD), and 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane (TATP) deposited on a steel surface. LEMS was also used to directly analyze composite propellant materials containing an explosive to determine the molecular composition of the explosive pellets at atmospheric pressure. Copyright © 2010 John Wiley & Sons, Ltd.