While a macroscopic understanding of most colloid and surface phenomena can be obtained from bulk property measurements, a deeper understanding of such imponant processes as adsorption, flotation and flocculation is possible only by the application of specialized spectroscopic and related techniques yielding molecular-level information. In chis paper, our recent efforts to explore the microscopic structures of surfactant and polymer layers on solids are outlined. In an attempt to delineate the microstructure of the polymer and surfactant adsorbates, computer-assisted tomographic (CAT) scan as well as small-angle neutron scattering (SANS) method are used in addition to luminescence, magnetic resonance and time-resolved resonance Raman spectroscopic studies. New information on the floc as well as adsorbed layer characteristics are presented. A simple method for studying short-term (< 1 min) adsorption kinetics of polymers on solids is also described.