Thermal-sensitive polymers have been tested on settling, compacting or dewatering of clays or oil sand tailings. However, not much attention has been paid to explore the effect of temperature on flocculating performance using thermal-sensitive polymers. In this study, poly(NIPAM-co-DMAPMA) was synthesized and employed to investigate the flocculating and re-flocculating performance of hydrophilic and hydrophobic particles at two specific temperatures; meanwhile settling and dewatering behaviors were also investigated. The results demonstrated that good flocculating performances were achieved at both room temperature (∼23 °C) and lower critical solution temperature (45 °C). Furthermore, larger flocs were formed at 45 °C as the copolymer was added. Floc strength and re-flocculating ability of the flocs were also intensified prominently at 45 °C. Additionally, settling and dewatering rates of suspensions were improved, and the moisture of filtered cakes was reduced when suspensions were at 45 °C. The phenomena could be justified by the phase transition of the copolymer from hydrophilicity to hydrophobicity as the temperature increased. There were much stronger adhesion forces between particles and higher adsorption amount of the copolymer onto solid surfaces at 45 °C. Therefore, the copolymer may be promising in solid-liquid separation to improve the floc size, floc strength, and settling and dewatering rate to achieve much lower moisture filtered cake.