The effects of biomolecular embedding on the photoinduced relaxation process of the DNA-minor-groove binder berenil, diminazene aceturate, are studied with quantum mechanics/molecular mechanics, QM/MM, calculations that employ the algebraic diagrammatic construction through second-order, ADC(2), for the quantum mechanical part and an atomistic polarizable embedding for the classical part. The lowest singlet excitation to the S1 state is a bright transition with a ππ* character and a perichromatic red shift, due to the interactions with the solvent and DNA. The excited-state relaxation pathway is a two-step mechanism, an N═N azo-bond stretch followed by a volume-conserving bicycle-pedal twist. The DNA confinement and the coupling to solvent molecules via hydrogen bonds lead, for the excited-state relaxation process, only to small deviations from the ideal bicycle-pedal relaxation. Because of its volume-conserving character, the S1 excited-state relaxation proceeds almost unhindered, even in a fully rigid minor-groove confinement. With a fully frozen DNA minor groove and solvent, the energy gap for deexcitation from S1 to the ground state increased to 2.0 eV compared to 0.16 eV in aqueous solution. When the relaxation of the first solvation shell is included, the relaxation process on the S1 potential energy surface proceeds to a region on the potential energy surface, where only a small gap to the ground-state potential energy surface remains, 0.43 eV. These results show that the solvent relaxation has a significant effect in controlling the energy gap between the ground and S1 electronically excited states, which explains the experimental observations of the fluorescence characteristics of berenil in DNA confinement.