Multiporphyrin-modified CdSe nanoparticles (CdSe-H2P) were prepared to elucidate the interaction between chromophores and luminescent semiconducting nanoparticles in the excited and ground states. The CdSe-H2P nanoparticles were obtained by place-exchange reactions of hexadecylamine-thiophenol-modified CdSe nanoparticles with porphyrin alkanethiols in toluene. The number of porphyrin molecules on the surface of a single CdSe nanoparticle increased with increasing reaction time to reach a saturated maximum of 21. The porphyrins as well as the core in CdSe-H2P can absorb UV/Vis radiation. Steady-state emission and emission-lifetime measurements reveal efficient energy transfer from the CdSe excited state to the porphyrins in the CdSe-H2P nanoparticles. The resulting porphyrin excited singlet state is not quenched by the CdSe core. These unique properties are in sharp contrast with those of multiporphyrin-modified metal and silica nanoparticles. Thus, semiconducting nanoparticle–multiporphyrin composites are highly promising as novel artificial photosynthetic materials.