The polymerization of MMA, at ambient temperature, mediated by dansyl chloride is investigated using controlled radical polymerization methods. The solution ATRP results in reasonably controlled polymerization with PDI < 1.3. The SET-LRP polymerization is less controlled while SET-RAFT polymerization is controlled producing poly(methyl methacrylate) (PMMA) with the PDI < 1.3. In all the cases, the polymerization rate followed first order kinetics with respect to monomer conversion and the molecular weight of the polymer increased linearly with conversion. The R group in the CTAs do not appear to play a key role in controlling the propagation rate. SET-RAFT method appears to be a simpler tool to produce methacrylate polymers, under ambient conditions, in comparison with ATRP and SET-LRP. Fluorescent diblock copolymers, P(MMA-b-PhMA), were synthesized. These were highly fluorescent with two distinguishable emission signatures from the dansyl group and the phenanthren-1-yl methacrylate block. The fluorescence emission spectra reveal interesting features such as large red shift when compared to the small molecule. © 2012 Wiley Periodicals, Inc.