Effect of MgO, CaSO4, and CaF2 addition on the formation of clinker minerals in portland cement have been investigated by measuring the amounts of free-CaO and C3S in the fired specimens and analyzing the Mg and S concentration in C3S and C2S. It was found that CaSO4 inhibited C3S formation but MgO addition offset this effect of CaSO4. MgO addition also enhanced the mineralizing effect of CaSO4+CaF2, resulting in the acceleration of C3S formation. It was suggested that Mg might inhibit the formation of sulphate compounds rim around C2S and thus C2S+CaOlongrightarrowC3S reaction was facilitated.