Adsorption behavior of polyvinylpyrrolidone (PVP) on sodium montmorillonite, a swelling clay mineral, was investigated in diluted solutions at an ionic strength of 0.01 M, representative of environmental soil solution conditions. Physicochemical methods such as microcalorimetry, light scattering absorbance, photon correlation spectroscopy, microelectrophoresis, X-ray diffraction, and sedimentation volume measurements were used to characterize the colloidal behavior of montmorillonite particles with various PVP loadings. The extent and properties of the adsorbed PVP train, loop, and end fractions in the particle-stabilizing process have been specified. The interaction study of chemicals such as anionic surfactant sodium dodecyl sulfate and nonionized 4-monochlorophenol as well as their mixture also underlines the importance of the PVP interfacial conformations for the adsorbent capacity of this organoclay.