This review article mainly surveys our research results of biphasic catalysis with thermoregulated ligands (TRL). Emphasis is given to the synthesis and property of the thermoregulated ligands, the general principles of thermoregulated phase-transfer catalysis (TRPTC) and thermoregulated phase-separable catalysis (TPSC). It also explores the applications of TRPTC and TPSC in the hydroformylation of higher olefins and CO selective reduction of nitroarenes. The introduction of TRPTC to biphasic system is free from the shortcomings of classical aqueous/organic two-phase catalysis, in which the application scope is restrained by the water solubility of the organic substrate. The biphasic catalysis with thermoregulated ligands was characterized by homogeneous catalysis coupled with convenient biphasic separation.