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 f(VBK,0) = 0.02-0.09, were synthesized using 10 mol % [tert-butyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino] nitroxide (SG1) relative to 2-([tert-butyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino]oxy)-2-methylpropionic acid (BlocBuilder) at 80 degrees C and 90 degrees C. Controlled polymerizations were observed, even with f(VBK,0) = 0.02, as reflected by a linear increase in number average molecular weight (M(n)) versus conversion X <= 0.6 with final copolymers characterized by relatively narrow, monomodal molecular weight distributions (M(w)/M(n) approximate to 1.5). Poly(DMAEMA-ran-VBK) copolymers were deemed sufficiently pseudo-"living" to reinitiate a second batch of N,N-dimethylacrylamide (DMAA), with very few apparent dead chains, as indicated by the monomodal shift in the gel permeation chromatography chromatograms. Poly(DMAEMA-ran-VBK) random copolymers exhibited tuneable lower critical solution temperature (LCST), in aqueous solution, by modifying copolymer composition, solution pH and by the addition of the water-soluble poly(DMAA) segment. (1)H NMR analysis determined that, in water, the VBK units of the poly(DMAEMA-ran-VBK) random copolymer were segregated to the interior of the copolymer aggregate regardless of solution temperature and that poly(DMAEMA-ran-VBK)-b-poly(DMAA) block copolymers formed micelles above the LCST. In addition, the final random copolymer and block copolymer exhibited temperature dependent fluorescence due to the VBK units. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 5270-5283, 2011