We measure UV photodissociation (UVPD) and UV-UV hole-burning (HB) spectra of dibenzo-15-crown-5 (DB15C5) complexes with alkali metal ions, M+center dot DB15C5 (M = Li, Na, K, Rb, and Cs), under cold (similar to 10 K) conditions in the gas phase. The UV-UV HB spectra of the M+. DB15C5 (M = K, Rb, and Cs) complexes indicate that there is one dominant conformation for each complex except the Na+center dot DBI5C5 complex, which has two conformers with a comparable abundance ratio. It was previously reported that the M+center dot(benzo-15-crown-5) (M+center dot B15C5, M = K, Rb, and Cs) complexes each have three conformers. Thus, the attachment of one additional benzene ring to the crown cavity of benzo-15-crown-5 reduces conformational flexibility, giving one dominant conformation for the M+ DB15C5 (M = K, Rb, and Cs) complexes. In the UVPD spectra of the K+center dot DB15C5, Rb+center dot DB15C5, and Cs+center dot DBI5C5 complexes, the S-1-S-0 and S-2-S-0 transitions are observed independently at different positions with different vibronic structures. The spectral features are substantially different from those of the K+center dot(dibenzo-18-crown-6) (K+center dot DB18C6) complex, which belongs to the C-2v, point group and exhibits exciton splitting with an interval of 2.7 cm(-1). The experimental and theoretical results suggest that in the M+center dot DB15C5 complexes the two benzene rings are not symmetrically equivalent with each other and the S-1-S-0 and S-2-S-0 electronic excitations are almost localized in one of the benzene rings. The electronic interaction energy between the two benzene chromophores is compared between the K+center dot DBISC5 and K+center dot DB18C6 complexes by quantum chemical calculations. The interaction energy of the K+center dot DB15C5 complex is estimated to be less than half of that of the K+center dot DB18C6 complex (similar to 30 cm(-1)) due to less suitable relative angles between the transition dipole moments of the two benzene chromophores in K+center dot DB1SC5.