A unique assembly approach was developed to fabricate conjugated polymer and photosensitizer-doped mesoporous silica nanoparticles with effective Förster resonance energy transfer (FRET) from poly[(9,9-di(3,30-N,N0-trimethylammonium)-propylfluorenyl-2,7-diyl)-alt-co-(1,4-phenylene)] (PFP) to porphyrin-based photosensitizers (PSs). PFP and silica nanoparticles form a complex through electrostatic interactions, and efficient energy transfer from PFP to porphyrin-based PSs occurs upon irradiation. This approach is stable, effective, and diversified. PS-doped mesoporous silica nanoparticles showed three- to four-fold enhanced emission with the excitation of the maximum absorption wavelength of PS in the presence of PFP in comparison to the case without PFP. Doping fluorescence dyes into the nonporous core and adjusting the content of PS conjugated with the shell can endow the silica nanoparticles with a combinational optical signal of dyes and PS. These silica nanoparticles exhibit further improved performance on the basis of enhanced energy transfer offered by light-harvesting conjugated polymers.