Recently, polymeric nanofibres have been considered for the rapid flocculation and dewatering of oil sands tailings. Apparently due to their fast initial interaction with the suspended fine particles, polymer nanofibres performed better than their parent water-soluble polymer solutions. To further understand this mechanism, a model study was conducted using kaolin suspensions and poly(acrylamide-co-diallyl dimethylammonium chloride) nanofibres and powders. The initial settling rate, supernatant turbidity, water recovery, capillary suction time, and solids content were measured to determine the effect of using nanofibres on solid-liquid separation. Nanofibres performed similarly to, or better than, equivalent polymer solutions in terms of initial settling rate and supernatant clarity at higher dosages and kaolin loadings. The kaolin studies showed that polymer nanofibres could absorb onto clay particles faster, and produce bigger flocs more rapidly, supposedly due to their high surface area to volume ratio. Our results indicate that polymer nanofibres, as well as polymer powders, may be successfully used to treat mature fine tailings produced from oil sands.