An approach is proposed for the quantum-chemical calculation of the structure and fluorescence spectra of exciplexes. The procedure involves the geometry optimization of exciplexes using the CIS method with empirical dispersion correction (CIS-D) and the subsequent single-point calculation of the transition energy using the CIS method with perturbative correction for double excitations (CIS(D)). Calculated fluorescence band positions for exciplexes of (dibenzoylmethanato)boron difluoride with substituted benzenes are in reasonable agreement with the experimental data.