A series of amphiphilic rod-coil diblock copolymers with it polyfluorene (PF) as it hydrophobic and light-emitting rod and a poly(N-isopropylacrylamide) (PNIPAAm) as a hydrophilic coil were prepared. Their micellar nanostructures and fluorescence properties were stimulated using Solvents, e.g., water and tetrahydrofuran (THF)/toluene (1:10 by volume), which were characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), atomic force microscopy (AFM), and fluorescence spectroscopy. A typical block copolymer P2 (M-n = 14400, M-w/M-n = 1.80, the PF weight fraction is 9.4%) in water exhibited micelles with the PNIPAAm block as the corona. whereas the polymer showed inverse micelles in mixed organic solvents of THF/toluene with PF as the corona. Such different nanostructures resulted in their different fluorescence properties. The fluorescence spectrum of 132 did not indicate aggregations of the PF chains ill the THF/toluene mixture. Blue emission with it high quantum yield (0.80) was observed. In contrast, strong aggregations of the PF chains were observed in the aqueous Solution, resulting in low quantum efficient (0.26) fluorescence. These results clearly demonstrated that the functionality of the P2 could be tuned through the solvent stimuli. The micelles of P2 were further used as nanocarriers to load a water-insoluble tetrakis(mesityl)porphyrin (H-2(Me-3)TPP) into its micellar aqueous solution. Efficient fluorescence resonance energy transfer (FRET) between the PF (donor) and H-2(Me-3)TPP (acceptor) (its high its 98% quenching of donor emission) was observed in their micellar solutions. Moreover, FRET contributes significantly to the efficiency of singlet oxygen generation from H-2(Me-3)TPP molecules (with all efficiency factor of 2 as compared to non-FRET micelles). This study provided it Feasible way to enable the application of water-insoluble porphyrin in aqueous Solution and enhance its singlet oxygen generation efficiency.