The time-dependent binding mode of a porphyrin dimer to poly[d(G-C)(2)] and poly[d(A-T)(2)] was investigated by spectroscopic methods including absorption and circular and linear dichroism (CD and LD) spectroscopy. Immediately after mixing with poly[d(G-C)(2)], the porphyrin dimer exhibited red-shift and hypochromism in the absorption spectrum and negative CD and LD spectra. With further red-shift in absorption, the CD and LD magnitude in the Soret region became increasingly negative over time. After it was stabilized, the magnitude of the reduced LD (LDr) in the Soret region was larger than that in the DNA absorption region, indicating that the second porphyrin was also intercalated. Following the rapid intercalation of the first porphyrin, the very slow intercalation of the second followed with first-order kinetics. In the poly[d(A-T)(2)] case, a bisignate CD spectrum was observed in the Soret region suggesting stacking of the porphyrins. The small alteration in the CD spectrum and increased absorbance, which followed the initial rapid spectral change, was of the second order. This alteration in the spectral properties was attributed to the conformational change of poly[d(A-T)(2)] near the binding site because the overall shape of the CD spectrum was conserved in spite of the changes in the absorption spectrum.