— The photobinding of psoralen and 8-methoxypsoralen to calf thymus DNA induced by 365 nm radiation has been measured for different concentrations of the furocoumarin and nucleotides. The results are consistent with the assumption that dark complexing of the furocoumarin to DNA is a pre-condition for photobinding, but do not exclude the possibility that the free furocoumarin participates in the reactions. The analysis with ‘large target’ diffusion theory indicates that photobinding should be inefficient for the free excited singlet state and competitive with reactions of the dark-complexed sensitizer for the free triplet state. The analysis indicates also that the diffusive reactions of singlet oxygen generated by the free furocoumarin can compete with photoadduct formation.