The spectroscopic and structural properties of surface crystallized Eu 3+ ions and Yb 3+ ions co-doped oxyfluoroborate glass ceramics have been studied. Luminescence measurements reveal higher cross-sections in the ceramic, on excitation with 464nm and 976nm laser radiations. Studies with polarized light as well as SEM images confirm crystallization in the ceramic and the XRD studies show that α-BaB 4 O 7 crystals are formed on the surface after annealing. These structural changes significantly alter the luminescence characteristics of Eu 3+ and Yb 3+ ions. A bright red emission from Eu 3+ ions is observed under 976nm excitation. The photophysics involved in this emission has been explained.