Rover mast-based stereo imaging, reflectance or emission spectra, and laser-induced breakdown spectroscopy (LIBS) provide powerful synergistic data sets for rapidly determining geologic setting, mineralogy, and elemental composition for rock and soil targets. We report results from hand specimen examination, multiple spectral reflectance (VISIR, 0.4--2.5 ¿m), and remote LIBS measurements for representative samples (basalt, iron oxides, altered rhyolite, and dolostone) collected during the May 2000 rover trials at Black Rock Summit, Nevada. Major findings are (1) reflectance data indicate the presence of olivine and montmorillonite for the basaltic sample, whereas LIBS data show variations with depth as an alumino-silicate coating is ablated and a basaltic composition is revealed beneath; (2) iron oxide reflectance data are dominated by goethite and hematite with the additional detection of hydrated cryptocrystalline SiO2 (an interpretation fully supported by the LIBS data); (3) VISIR reflectance data for rhyolite show significant alteration to kaolinite, an inference that would be difficult to make from LIBS data alone; (4) dolostone reflectance data show dominantly dolomite with minor iron oxides, inferences confirmed through analyses of LIBS data; and (5) LIBS data acquired for samples as a function of depth and spatial location significantly aid in understanding the extent of sample coatings and compositional and mineralogical diversity. Given the hand specimen examination and results from joint analysis of the two rapid-acquisition spectral techniques, a scenario for acquisition and analysis of mast-based imaging reflectance or emission spectroscopy and LIBS is presented within the context of the scientific objectives for the Mars Exploration Program.