A series of random copolymers and block copolymers containing water-soluble 4AM and fluorescent VAK are synthesized by NMP. The homopolymerizations of 4AM and VAK and 4AM/VAK random copolymerization are performed in 50 wt% DMF using 10 mol% SG1, resulting in a linear increase in versus conversion, and final polymers with narrow molecular weight distributions ( < 1.4). Reactivity ratios rVAK = 0.64 ± 0.52 and r4AM = 0.86 ± 0.66 are obtained for the 4AM/VAK random copolymerization. In addition, a poly(4AM) macroinitiator is used to initiate a surfactant-free suspension polymerization of VAK. After 2.5 h, the resulting amphiphilic block copolymer has = 12.6 kg · mol−1, = 1.48, molar composition FVAK = 0.38 with latex particle sizes between 270 and 475 nm.