The flocculation and solid/liquid separation of four well-characterized kaolinites (2 well, 2 poorly crystallized) have been studied for comparison of surface structure (SEM), aggregate structure during flocculation (cryo-SEM), settling rate, and bed density (with raking). It is shown that major differences in these properties are largely due to crystallinity and consequent surface structure of the extensive (larger dimension "basal") face. Well-crystallized kaolinites, with higher Hinckley indices and lower aspect ratios, have relatively smooth, flat basal surfaces and thicker edge planes promoting both effective initial bridging flocculation (largely edge-edge) and structural rearrangement to face-face during the raking process. This results in faster settling rates and more compact bed structures. Poorly crystallized kaolinites, with low Hinckley indices and high aspect ratios, exhibit ragged, stepped structures of the extensive face with a high proportion of nanosized islands forming cascade-like steps (i.e., multiple edges) contributing up to 30% of the specific surface area and providing flocculant adsorption sites (hydroxyl groups) across this extensive face. This leads to bridging flocculation taking place on both edge and extensive ("basal") planes, producing low-density edge-face structures during flocculation which leads to slow settling rates and poor bed densities. In particular, the complex surface morphology of the poorly crystallized kaolinites resists the transformation of edge-face structures to dense face-face structures under shear force introduced by raking. This results in low sediment density for poorly crystallized kaolinites. The studies suggest that the main influence on settling rates and bed densities of kaolinites in mineral tailings is likely to be related to the crystallinity and surface morphology of the kaolinite. They also suggest that interpretation of kaolinite behavior based on models of a flat (001) basal plane and edge sites only at the particle boundaries is not likely to be adequate for many real, less-crystallized kaolinites.