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 $\overline {M} _{{\rm n}} $ versus conversion, and final polymers with narrow molecular weight distributions ($\overline {M} _{{\rm w}} /\overline {M} _{{\rm n}} $?<?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 $\overline {M} _{{\rm n}} $?=?12.6?kg center dot mol-1, $\overline {M} _{{\rm w}} /\overline {M} _{{\rm n}} $?=?1.48, molar composition FVAK?=?0.38 with latex particle sizes between 270 and 475?nm.