Spectral properties, energy structure, and electronic processes in DNA, poly (dAdT)(2), d(CCCGGGTTTAAA), d(ATC), d(AT), dGMP, dAMP, dCMP, dTMP were studied. The DNA lowest excited electronic singlet and triplet levels are connected with guanine and adenine bases, correspondingly. The DNA fluorescence is close to a linear combination of the guanine and cytidine emissions and connected, to a greater extent, with the singlet energy transfer to these bases. The origin of the DNA phosphorescence is associated with AT-sequences that are traps of triplet excitations in DNA. The triplet energy transfer to these centers and adenine bases (that are most photostable) leads to the DNA self-protection against a damage induced by electronic excitations of DNA.