A cationic thermal sensitive polymer, poly[N-isopropylacrylamide-co-N-[3-(Dimethylamino)propyl]methacrylamide] (CP) of different molar ratios, known as CP05 and CP10 was synthesized in-house. By doping aluminum hydroxide (Al(OH)3) colloids into CP during the polymerization process, a novel hybrid polymer flocculant, Al-CP05, was synthesized. All flocculants showed a temperature and pH dependent coil-globule transition, and could alter the surface charge of fine kaolinite particles. For comparison, a coagulant and flocculant mixture was prepared by blending CP05 and Al(OH)3, which was called {CP05+Al}. The synthesized flocculants or blends were applied to kaolinite suspensions and laboratory oil sands extraction tailings to evaluate their settling and filtration performances. Al-CP05 was shown to provide the most effective flocculation on both kaolinite suspensions and tailings while its temperature sensitivity was partially lost in filtration of tailings. CP05 and CP10 showed similar flocculation performance on both kaolinite suspensions and tailings which was less effective than {CP05+Al} blends.