The conversion of glass to a hydroxyapatite (HA) material in an aqueous phosphate solution is used as an indication of the bioactive potential of the glass, as well as a low temperature route for preparing biologically useful materials. In this work, the effect of varying concentrations of pyrophosphate ions in the phosphate solution on the conversion of a calcium–lithium–borate glass to HA was investigated. Particles of the glass (150–355 μm) were immersed for up to 28 days in 0.25 M K2HPO4 solution containing 0–0.1 M K4P2O7. The kinetics of degradation of the glass particles and their conversion to HA were monitored by measuring the weight loss of the particles and the ionic concentration of the solution. The structure and composition of the conversion products were analyzed using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. For K4P2O7 concentrations of up to 0.01 M, the glass particles converted to HA, but the time for complete conversion increased from 2 days (no K4P2O7) to 10 days (0.01 M K4P2O7). When the K4P2O7 concentration was increased to 0.1 M, the product consisted of an amorphous calcium phosphate material, which eventually crystallized to a pyrophosphate product (predominantly K2CaP2O7 and Ca2P2O7). The consequences of the results for the formation of HA materials and devices by the glass conversion route are discussed.