In this paper, self-assembled polymeric toroids formed by a temperature-driven process are reported. Rhodamine B (RhB) end-capped poly(N-isopropylacrylamide) (PNIPAAm) demonstrating a lower critical solution temperature (LCST) is prepared. In a two-phase system, the polymer in the aqueous phase could move to the chloroform phase on raising the temperature above its LCST. This temperature-driven process results in the formation of polymeric toroids in the chloroform phase, and the strategy affords a new pathway to toroidal self-assembly of polymers. Moreover, the photoluminescent behavior of the RhB end-capped PNIPAAm species formed by the process is also studied and discussed.