Complex films of 5,10,15,20-tetrakis(4-N-methylpyridyl)porphine tetra(p-toluenesulfonate) (TMPyP) and deoxyribonucleic acid (DNA) were formed by sequential deposition of TMPyP and DNA from aqueous solution onto quartz substrates. The deposition was monitored by absorption spectroscopy. It revealed that the DNA-TMPyP complex film is uniformly assembled layer-by-layer and the net charge of the dye is important in forming the DNA-dye film. The resulting DNA-dye complex multilayer films were characterized by UV-vis spectroscopy, fluorescence spectroscopy and fluorescence lifetime measurements. It has been found that TMPyP can either bind to the DNA electrostatically or intercalate into the base pairs. The relative ratio of the TMPyP intercalating into the DNA in the film is smaller than that in solution.