We prepared cold-setting cement with metakaolin from kaolin dehydrated at 800 ℃ and phosphate, and studied the phase composition, microstructure and setting reaction mechanism of the cementing material by means of infrared spectroscopy, thermogravimetry, X-ray diffraction, and scanning electron microscopy. The metakaolin-phosphate cement is predominantly amorphous, where the phases responsible for chemical setting are mainly amorphous aluminophosphate hydrates. The reactivity of metakaolin depends on the particle size. Metakaolin particles of 1.75 μm in D50 have an acid dissolution index up to 18.45%, and the reaction with phosphate at room temperature to form metakaolin-phosphate cement takes only 6 h. The so obtained cement shows a compressive strength of 92.5 MPa after 7 d and keeps its amorphous phase at 1 000 ℃, demonstrating better bonding and mechanical properties and higher stability at a medium or high temperature.