The performance of alkali-activated phosphor slag-fly ash cement with different phosphor slag/fly ash proportions was studied, and the pore and microstructure of the hardened pastes were analyzed by mercury intrusion porosimetry and scanning electron microscope. The results show that alkali-activated phosphor slag cement has normal setting performance, which is different from that of alkali-activated blast furnace slag cement. The compressive strengths of the cement at 3 d and 28 d reach as high as 30.9 MPa and 98.8 MPa, respectively, and the flexural strengths are lower compared with ordinary portland cement. Adding 0-30% (in mass)fly ash into the alkali-phosphor slag system will slightly increase the setting time, however it will reduce the compressive strength,and improve the flexural strength. The corrosion resistance and freeze/thaw resistance of alkali-activated cement are much better, and the drying shrinkage rate is much greater than ordinary portland cement. Substituting phosphor slag partly with fly ash reduces the drying shrinkage to some extent. The hardened alkali-activated phosphor slag-fly ash cement paste is very dense due to very low porosity and a small mean pore diameter.