The spectrometers on the Mars Science Laboratory (MSL) ChemCam instrument were used in passive mode to record visible/near-infrared (400–840 nm) radiance from the martian surface. Using the onboard ChemCam calibration targets’ housing as a reflectance standard, we developed methods to collect, calibrate, and reduce radiance observations to relative reflectance. Such measurements accurately reproduce the known reflectance spectra of other calibration targets on the rover, and represent the highest spatial resolution (0.65 mrad) and spectral sampling (<1 nm) visible/near-infrared reflectance spectra from a landed platform on Mars. Relative reflectance spectra of surface rocks and soils match those from orbital observations and multispectral data from the MSL Mastcam camera. Preliminary analyses of the band depths, spectral slopes, and reflectance ratios of the more than 2000 spectra taken during the first year of MSL operations demonstrate at least six spectral classes of materials distinguished by variations in ferrous and ferric components. Initial comparisons of ChemCam spectra to laboratory spectra of minerals and Mars analog materials demonstrate similarities with palagonitic soils and indications of orthopyroxene in some dark rocks. Magnesium-rich “raised ridges” tend to exhibit distinct near-infrared slopes. The ferric absorption downturn typically found for martian materials at <600 nm is greatly subdued in brushed rocks and drill tailings, consistent with their more ferrous nature. Calcium-sulfate veins exhibit the highest relative reflectances observed, but are still relatively red owing to the effects of residual dust. Such dust is overall less prominent on rocks sampled within the “blast zone” immediately surrounding the landing site. These samples were likely affected by the landing thrusters, which partially removed the ubiquitous dust coatings. Increased dust coatings on the calibration targets during the first year of the mission were documented by the ChemCam passive measurements as well. Ongoing efforts to model and correct for this dust component should improve calibration of the relative reflectance spectra. This will be useful as additional measurements are acquired during the rover’s future examinations of hematite-, sulfate-, and phyllosilicate-bearing materials near the base of Mt. Sharp that are spectrally active in the 400–840 nm region.