Temperature-responsive hyperbranched polymers containing primary amines as pendent groups have been synthesized for solid-liquid separation of kaolinite clay suspension. The effects of temperature, polymer charge density, and polymer architecture on particle flocculation have been investigated. Suspensions treated with the temperature-responsive amine-based hyperbranched polymers showed remarkable separation of the fine particles at a low polymer dosage of 10 ppm and at testing temperatures of 40 °C. In comparison to other polymers studied (linear and hyperbranched homopolymers and copolymers), the temperature-responsive amine-based hyperbranched copolymers showed better particle flocculation at 40 °C, as evidenced by the formation of a thinner sediment bed without compromising the amount of clay particles being flocculated. This superior solid-liquid separation performance can be explained by the hydrophobic interaction of PNIPAM segments on particle surfaces or the capture of additional free particles or small floc due to the exposure of buried positive charges (because of the phase separation of the hydrophilic amines and hydrophobic PNIPAM part) at temperatures above the lower critical solution temperature (LCST).