Photophysical properties of water-soluble porphyrin were studied in aqueous solutions with/without DNA and in DNA solid films. Ultrathin films were prepared from aqueous DNA solutions by a spin-coating method on glass or on gold nanoparticles (AuNPs). Remarkable enhancement of phosphorescence was observed for porphyrin immobilized in DNA films spin-coated on AuNPs, which was attributed to the electric field enhancement and the increased radiative rate by localized surface plasmon resonance of AuNPs.