This study utilized a novel in situ fiber-optic Raman probe to continuously monitor the hydration progress of tricalcium silicate (C3S) and dicalcium silicate (C2S) without the need for sampling, from early hydration stage to later stages, and from fresh to hardened states of paste samples. By virtue of the remarkable ability of this technique in characterizing either dry or wet and crystalline or amorphous samples, the hydration processes of C3S and C2S pastes with different water-to-solid (w/s) ratios could be monitored from the start of the hydration reaction. The main hydration products, calcium silicate hydrate (C–S–H) and portlandite/calcium hydroxide (CH), have been successfully identified and continuously monitored for variations in their respective amounts in situ. The effect of w/s ratio on the hydration processes of C3S and C2S pastes was also considered. Meanwhile, the x-ray diffraction (XRD) and thermogravimetric analysis (TGA) results showed a great correlation with the in situ Raman test results about hydration products, which demonstrated the reliability of this technology. Moreover, the signal-to-noise ratio (SNR) of this Raman probe is significantly superior to existing technologies for in situ fiber-optic Raman spectroscopy. This remote fiber-optic Raman probe enables the use of Raman spectroscopy in future construction projects for on-site monitoring and evaluation of health conditions and performance of concrete structures.