Investigating the interaction of silicon and aluminum oxides with aqueous solutions containing chromium ions is important for environmental studies and technological applications. We review bulk thermodynamic adsorption experiments of trivalent and hexavalent chromium with various natural and synthetic surfaces. Subsequently, we review two optical probes aimed at characterizing sub-surface and molecular interactions associated with the adsorption process. Laser-scanning confocal fluorescence microscopy has been used to investigated silica gel/chromium interactions and particle morphology. Surface second-harmonic generation spectroscopy has been explored to study chromium adsorption at the quartz/water interface.