Alite (Ca₃SiO₅: C₃S^*) and calcium aluminate (Ca₃Al₂O₆: C₃A) are the major phases in Portland cement, which have an essential role in the development of early age properties. The effects of gypsum content, fineness, and Na₂SO₄ addition on the early-stage hydration kinetics are investigated for polyphase (co-sintered) Ca₃SiO₅-Ca₃Al₂O₆ model systems using calorimetry, X- ray diffraction, thermal analysis, and solid-state ²⁷Al and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy. The results demonstrate that the hydration of C₃A significantly affects the hydration of C₃S. The C₃S and C₃A hydration is hindered considerably in severely over-sulfated systems (where C₃A hydration is suppressed due to a very high gypsum content) and systems with additional Na₂SO₄. Although there is a considerable amount of Al incorporation in the C-S-H phase, no clear trends with respect to gypsum content, hydration age or Na₂SO₄ addition are observed for the Al_IV/Si ratios of the C-S-H phase determined from ²⁹Si NMR. With the addition of Na₂SO₄, recrystallization of ettringite from the AFm phases is postponed from 1 day to 7 days. *Cement chemistry notation: C-CaO, S-SiO₂, A-Al₂O₃, (Formula presented.) -SO₃, N-Na₂O.