The nanoparticle-based fluorescence resonance energy transfer (FRET) systems have recently attracted considerable attention due to some of their advantages; however, these systems are structurally more complicated than that of small molecule systems, and the energy transfer behavior for particle systems has been seldom investigated. In this study, we synthesized a series of ABC triblock copolymers that contain hydrophilic poly(ethylene oxide) (PEO), hydrophobic poly(styrene) (PS) and photochromic poly(2-(3-(3',3'-dimethyl-6-nitrospiro(indoline-2',2-[2H-1]benzopyran)-1'-yl)propanoylo-xy)ethyl methacrylate) (PSPMA) blocks by using the sequential two-step atom transfer radical polymerization (ATRP). The amphiphilic micelles made from these copolymers can incorporate a hydrophobic fluorescent dye, the nitrobenzoxadiazolyl derivative (NBD), thus forming a water dispersible energy transfer system with the fluorescent dye NBD as the donor and spiropyran moieties as the potential acceptor. The spectral properties of NBD/triblock copolymers with varied PS block lengths and PSPMA block lengths have been investigated; the results indicate that the length of PS block in triblock copolymers can affect the energy transfer efficiency of the micelle-based fluorescence modulation system, the micelles with moderate PS block length are preferable for forming FRET system with higher energy transfer efficiency, and short PSPMA blocks (less than 5 repetition units) are enough for efficient energy transfer.