Structural aspects of dilute homoionic Li-, Na-, K-, and Cs-montmorillonite (M-montmorillonite) particle suspension (1 g/L) under low-electrolyte-concentration (0.1 mM MCl) conditions were characterized by static (absorbance or turbidity) and dynamic (photon correlation spectroscopy) light-scattering methods as well as the adsorption behaviors of nonionic polyvinylpyrrolidone (PVP) mol wt 5,000 g/mol (LMW PVP) and mol wt 400,000 g/mol (HMW PVP). Taking Li-montmorillonite as a reference for a single plate particle, a particle size increase and a surface accessibility decrease to polymer adsorptions were measured along the Li, Na, K, and Cs series. The results are related to the existence of montmorillonite quasicrystals or tactoids in diluted suspension, whose stability increases along the same cation series. Molecular weight effects on the PVP surface accessibility are discussed in terms of permeation properties of the different M-montmorillonite particles. Modeling the results calculates an average number of plates in montmorillonite quasi-crystals and the surface area distribution of ultramicropores <0.7 nm and pores >0.7 nm in M-montmorillonite particles. It can also be demonstrated by applying hydrodynamic and electrokinetic methods that the measured high absorbance or turbidity increase of PVP-loaded montmorillonite particles is not due to aggregation phenomena but to a PVP contribution in the light-scattering intensity.