A pulse photobleaching methodology wherein a monochromatic illumination (e.g., laser illumination) having a higher power intensity (photobleaching power) just below the photodamage threshold of a luminescent sample is initially used to significantly attenuate sample luminescence without photothermally destroying the sample material. Thereafter, the laser power density may be reduced to a significantly lower level (analytical power level) to carry out spectroscopic measurements (e.g., collection of Raman scattered photons) on the sample. In one embodiment, the laser illumination wavelength remains the same despite changes in laser power intensity. Some figures-of-merit may be computed from optical measurements made at the analytical power level to guide the photobleaching process. Sample-dependent combinations of laser power density and short exposure times may be obtained to significantly expedite photobleaching to assist in collection of sample spectral data in the field without a long wait. Portable spectroscopy systems employing pulse photobleaching may be devised for expeditious collection of spectral data from luminescent samples in the field.