Cement-limestone powder pastes added with 10% magnesium sulfate, sodium sulfate, and calcium sulfate respectively were stored in water at (5±2) °C to accelerate thaumasite formation. The pastes were inspected visually at intervals. And the formation of thaumasite was identified and confirmed by X-ray diffraction (XRD), infrared spectroscopy (IR), and nuclear magnetic resonance spectroscopy (NMR). The results show that internal adding sulfate in cement-limestone powder paste is an efficient way to accelerate thaumasite formation, and the accelerated effect is magnesium sulfate> sodium sulfate> calcium sulfate. Cement-limestone paste containing 10% magnesium sulfate totally turns into grey-white mushy materials after 6 months immersion, and products are mainly thaumasite and gypsum. In addition, the amount of thaumasite increases along with time of internal sulfate attack in 15 months. XRD, IR, and NMR are powerful and reliable tools for identification of thaumasite in cement-based materials.