The glass transition temperature increases and the thermal expansion coefficient and density decrease with increasing B2O3 concentration in a series of (100-x)(50BaO-50P(2)O(5))-xB(2)O(3) where x = 0-10 mol% for bulk samples. According to Raman spectroscopy, the bulk BaO-P2O5-B2O3 (BaP-B) glasses consist of metaphosphate Q(2) units with ring-type metaborate, diborate, and PO4-BO4 groups. X-ray photoelectron spectroscopy results reveal qualitatively that P-O-B bonds are formed at the surface of BaP-B glass samples ground in laboratory air over 6 mol% B2O3 only. The P-O-B bonds are related to the suppression of the crystallization of powdered BaP-B glasses with > 6 mol% B2O3 during differential thermal analysis.