The atomic scale structure of sodium borophosphates made by the sol–gel method is compared to those made by the melt-quench method. It is found that although the sol–gel generated materials have a higher tendency towards crystallization, they nevertheless show a qualitatively similar crystallization trend with composition to their melt-quench analogues; the progressive introduction of boron oxide into the phosphate network initially inhibits then promotes crystallization. At the composition associated with the most stable amorphous sodium borophosphate (20 mol% boron oxide), it is found that the atomic scale structure of the sol–gel synthesized network glass is almost identical to that of the corresponding melt-quenched one.