The influence of tricalcium aluminate (3CaO·Al2O3) phase doping on in vitro biocompatibility and bioactivity of calcium aluminate (CaO·Al2O3) based bone cement has been investigated. It is demonstrated that the presence of approximately 25% tricalcium aluminate in the bone cement remarkably improves the bioactivity, yet still retains desirable mechanical strength and biocompatibility. An intermediary compound layer such as Ca3Al2(OH)12 was formed on the surface of the doped sample onto which hydroxyapatite (HAp) began to form soon, after only 2 days of immersion in a simulated body fluid solution. This is about seven-fold acceleration in the HAp formation over undoped calcium aluminate cement on which it took approximately15 days to nucleate the HAp phase. The depth of the HAp-containing layer after60 days of soaking was as much as 85 μm, about an order of magnitude more than the undoped calcium aluminate cement. The dramatically accelerated nucleation and growth of hydroxyapatite caused by the presence of tricalcium aluminate is attributed to the occurrence of intermediate layer materials such as Ca3Al2(OH)12, which most likely acts as the nuclei for HAp formation. This doped bone cement can be useful for injectable orthopedic applications, as the setting time for hardening has also been significantly reduced (by a factor of at least 4) to a practical regime of tens of minutes.