Bismuth borate glasses with Bi(2)O(3) concentration of 20-66 mol% were prepared by melt quenching and devitrified by heat treatment above their glass transition temperatures. All glasses show a strong tendency towards crystallization on annealing that increases with Bi(2)O(3) concentration. The crystalline phases formed on devitrification were characterized by FTIR absorption spectroscopy and DSC measurements. Our studies reveal that phases produced in glasses are strongly determined by initial glass composition and the two most stable crystalline phases are: Bi(3)B(5)O(12) and Bi(4)B(2)O(9). The metastable BiBO(3) phase can also be formed by devitrification of glass with 50 mol% of Bi(2)O(3). This phase is, however, unstable and decomposes into Bi(3)B(5)O(12) and Bi(4)B(2)O(9) on prolonged heat treatment.