The ring-opening polymerization (ROP) of tetrahydrofuran (THF) and ε-caprolactone (CL) was performed at 160 oC for 2 hr under N2 ambiance by using two different dyes such as fluorescein (Flur) and rhodamine6G (R6G) as novel initiators. The structure of the dye centered diblock copolymers was concluded by analyzing the NMR spectra. The melt transition temperature and thermal stability of the polymers were concluded by DSC and TGA. The FT-IR spectra concluded the structure of the dye grafted homopolymer and diblock copolymers. The increase in molecular weight (Mw) of the dye-centered diblock copolymer was concluded by the GPC measurement. The conjugation of dye with the polymer backbone was carried out by a single-step method.