Block copolymer micelles have been prepared with a dithiomaleimide (DTM) fluorophore located in either the core or shell. Poly(triethylene glycol acrylate)-b-poly(tertbutyl acrylate) (P(TEGA)-b-P(tBA)) was synthesized by RAFT polymerization, with a DTM-functional acrylate monomer copolymerized into either the core forming P(tBA) block or the shell forming P(TEGA) block. Self-assembly by direct dissolution afforded spherical micelles with R-h of ca. 35 nm. Core-labeled micelles (CLMs) displayed bright emission (Phi(f) = 17%) due to good protection of the fluorophore, whereas shell-labeled micelles (SLMs) had lower efficiency emission due to collisional quenching in the solvated corona. The transition from micelles to polymer unimers upon dilution could be detected by measuring the emission intensity of the solutions. For the core-labeled micelles, the fluorescence lifetime was also responsive to the supramolecular state, the lifetime being significantly longer for the micelles (tau(Av,I) = 19 ns) than for the polymer unimers (tau(Av,I) = 9 ns). The core-labeled micelles could also self-report on the presence of a fluorescent hydrophobic guest molecule (Nile Red) as a result of Forster resonance energy transfer (FRET) between the DTM fluorophore and the guest. The sensitivity of the DTM fluorophore to its environment therefore provides a simple handle to obtain detailed structural information for the labeled polymer micelles. A case will also be made for the application superiority of core-labeled micelles over shell-labeled micelles for the DTM fluorophore.