Polyfluorenes and their nanoparticles are of interest because of their desirable photoluminescent properties. Here, we report the synthesis of a polyfluorene macromonomer p-[poly(9,9-dihexylfluorene-2,7-diyl] styrene (PFS) and their narrow polydispersity PFS-containing random copolymers with t-butyl acrylate [P(PFS-r-t-BA)s], i.e. via both reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP). The acid hydrolysis of P(PFS-r-t-BA) gives the corresponding amphiphilic P(PFS-r-acrylic acid) [P(PFS-r-AA)] polyelectrolytes, which self-assemble into photoluminescent nanoparticles in aqueous solutions. The P(PFS-r-AA) was shown to act as a scaffold for the incorporation of other pigments, which allowed tunable emissions via varying pigment combinations by Förster resonance energy transfer. The occurrence of strong white light emission was demonstrated.