This article describes a new class of triple thermoresponsive ‘schizophrenic’ diblock copolymer that undergoes transitions from conventional micelles (or vesicles) via unimers to reverse micelles (or vesicles) and finally to a precipitated state upon heating. The various transition temperatures of this copolymer could be well controlled by the concentration of trivalent anion and pH that control the upper critical solution temperature of the poly(dimethylaminoethyl methacrtylate) (PDMAEMA) block or the type of poly(methoxy oligoethylenegylol methacrylate) (PmOEGA) to vary the lower critical solution temperature.