We report on the synthesis of heterotelechelic alpha,omega-dyelabeled polystyrene and poly(methyl methacrylate) via a combination of site-specific atom transfer radical polymerization (ATRP) and click chemistry. By using the advantages of the living polymerization characteristics and a robust coupling efficiency, the Forster/fluorescence resonance energy transfer (FRET) pairs (i.e., carbazolyl and anthryl) were dictated to be at the near-stoichiometric chain ends. The distribution of the end-to-end distance was well described by the energy transfer response of the fluorescent groups between chain ends, which is in reasonable agreement with Gaussian statistics. The synthetic approach described here provides an opportunity to prepare polymeric materials with customized responsive elements and in-depth insight into the statistical scaling dimension of polymers.