A controlled, pseudo-“living” polymerizations of a series of poly(2-(dimethylamino)ethyl methacrylate-ran-9-(4-vinylbenzyl)-9H-carbazole) poly(DMAEMA-ran-VBK) random copolymers, with VBK molar feed compositions fVBK,0 = 0.02–0.09, was accomplished by using SG1 based commercially available initiator known as BlocBuilder. In all cases, a linear increase in number average molecular weight (Mn) versus conversion X ≤ 0.6 with and a final copolymers characterized by relatively narrow, monomodal molecular weight distributions (Mw/Mn ≈ 1.5) was obtained. Poly(DMAEMA-ran-VBK) copolymers were also capable of reinitiating a second batch of N,N-dimethylacrylamide (DMAA), with very few apparent dead chains. Poly(DMAEMA-ran-VBK) random copolymers exhibited tuneable lower critical solution temperature, in aqueous solution, by modifying copolymer composition, solution pH and by the addition of the water-soluble poly(DMAA) segment. In addition, the final random copolymer and block copolymer exhibited temperature-dependent fluorescence due to the VBK unit.