Ozonolysis of alkenes in the troposphere produces Criegee intermediates, which have eluded detection in the gas phase until very recently. This laboratory has synthesized the simplest Criegee intermediate within a quartz capillary tube affixed to a pulsed valve to cool and isolate CH(2)OO in a supersonic expansion. UV excitation resonant with the B (1)A' ← X (1)A' transition depletes the ground-state population of CH(2)OO, which is detected by single-photon ionization at 118 nm. The large UV-induced depletion (approaching 100%) near the peak of the profile at 335 nm is indicative of rapid dissociation, consistent with the repulsive B (1)A' potential along the O-O coordinate computed theoretically. The experimental spectrum is in very good accord with the absorption spectrum calculated using the one-dimensional reflection principle. The B ← X spectrum is combined with the solar actinic flux to estimate an atmospheric lifetime for CH(2)OO at midday on the order of ∼1 s with respect to photodissociation.