The luminescence properties of Sm3+ ions in YAl3B4O12 were studied upon synchrotron excitation in the 3.8-11 eV region. In addition to the 4f -> 4f excitation bands, the excitation spectra of the Sm3+ emission contain broad bands at 6.1 and similar to 7.0 eV. These bands are attributed to charge transfer transition in Sm3+-O2- complexes and 4f -> 5d transition of Sm3+ ions, respectively. The optical absorption edge of YAl3B4O12 was determined at 7.3 eV. A comparison with the results of electronic structure calculations on YAl3B4O12 is also made.