Silicate-substituted calcium phosphates have been shown to result in enhanced biological OF performance compared to the corresponding, silicate-free, calcium phosphates. We have produced a range of silicate-substituted alpha-TCP compositions using two different synthesis methods and two different substitution mechanisms. Single phase compositions were only observed for a silicate substitution of 1.3 wt% by both solid state synthesis and aqueous precipitation synthesis, although the latter was the result of a design composition with a higher silicate substitution (3 wt%). The silicate substitution resulted in small changes in the unit cell parameters of the alpha-TCP. More importantly, this small level of silicate substitution had a strong effect on the thermal stability of the alpha-TCP phase, with the silicate substitution stabilising the alpha-polyrnorph to lower temperatures. This has an immediate advantage in that the quenching conditions are not as critical for the production of silicate-substituted alpha-TCP compositions compared to silicate-free alpha-TCP.