AbstractApplication of calcium aluminate cement in construction faces the challenges of high manufacturing cost and volumetric instability associated with hydrates conversion. This work introduces a newly developed high‐performance Ca20Al26Mg3Si3O68 (Q phase)‐metakaolin (MK) composite binder. The influence of MK on the conversion and strength development of Q phase paste cured at 40°C was investigated. The mechanism of MK on the stability of synthetic hydrate was studied by solution chemistry, XRD, and NMR. The pure Q phase paste experiences a significant strength reduction due to hydrates conversion, whereas the Q phase paste containing 15% MK exhibits a continuous increase in strength. MK promotes the formation of CAH10, contributing to the refinement of pore structure and enhanced mechanical property. The AlV and AlIV dissolved from MK increase the concentration in the pore solution, and then the solubility of CAH10 decreases due to the common‐ion effect, thus inhibiting the subsequent precipitation of C3AH6. In addition, the release of dissolved alumina from MK considerably impedes silica dissolution, and consequently, the formation of C2ASH8 is hindered at a higher content of MK.