The phenomena of single-layer graphene resonant photoluminescence and Raman radiation are discussed taking into account the photo-generated electron–hole Coulomb interaction. On the base of general principles of a many-particle interactions and the interband resonance optical transitions a photon radiation new mechanism (Coulomb mechanism) is proposed. Through Stokes 2D’-mode particular case analysis has shown that the graphene photoluminescence and the resonant Raman radiation are characterized by the same frequency shifts. Probabilities of resonance photo-radiation processes have been presented where the electron–hole Coulomb attraction has been taken into account. The probabilities are the same fourth-order small values. The weak photo-radiation Coulomb mechanism has a common character. It is applicable to both zero and nonzero band gap crystals.