New insights into the chemistry of alumino-phosphate solutions are provided in this contribution. In a first part, a solution with a P/Al molar ratio of 3.2 was prepared for the first time. The binders obtained at 500 and 700 °C were compared to those obtained with the 3 and 3.5 P/Al molar ratio solutions in order to determine the impact of moderate P2O5 excess on the final phosphate ceramic nature. In a second part, the widely used P/Al=3 solution was heat-treated at 500 °C using different heating rates (0.2, 1, and 10 °C/min) to determine how this parameter modifies the final phosphate ceramic composition. Our data show that moderate P2O5 excess is sufficient to obtain binders with a high amount of stable cubic aluminium metaphosphate compound at 700 °C but not at 500 °C, where significant P2O5 excess is mandatory. We also show that slow heating favors the formation of cubic aluminium metaphosphate compound at 500 °C.