Novel tryptophan-based block copolymers with unique self assembled structures, chiroptical properties, and sensing functionality were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization of a tryptophan-containing acrylamide, N-acryloyl-L-tryptophan (A-Trp-OH). Polymerization of A-Trp-OH using a suitable chain transfer agent (CTA) proceeded in a controlled fashion, as confirmed by the relatively narrow polydispersity of the products and a molecular weight that could be controlled by the monomer-to-CTA molar ratio. Hydrophilic polymers obtained by RAFT polymerization of N,N-dimethylacrylamide, poly(ethylene glycol) methyl ester methacrylate, and N-acryloy1-4-trans-hydroxy-L-proline were used as macro-CTAs. Chain extension of these hydrophilic macro-CTAs with A-Trp-OH was well controlled under the appropriate conditions to afford block copolymers with "as-designed" chain structures and relatively low polydispersities. The formation. of micelles consisting of a hydrophobic core of poly(A-Trp-OH) and a hydrophilic shell was observed in aqueous solution and affected the optoelectronic properties of the polymer. We further investigated the chiroptical and sensing properties of the block Copolymers by dynamic light scattering, UV-vis and fluorescence Spectroscopy, and,circular dichroism measurements. We present a new example of amino acid-based polymeric fluoride ion (F-). probes in Which micelles self-assembled from .:these block copolymers serve as enhanced ratiometric fluorescent and chiroptical F- sensors possessing characteristic detection capabilities in aqueous and organic media.