The change of the evaporable water content in the early hydration process of cement paste with different water-to-cement ratios was monitored by low field nuclear magnetic resonance (LF-NMR) relaxometry. The hydration degree and gel/space ratio were accordingly calculated and analyzed. The test results show that the first derivative curves of the transverse magnetization are in good agreement with the known five stages of cement hydration process at an early age. The initial and final setting times of the cement paste are closely related to the times the gel/space ratio reaches a fixed value. The early compressive strength of the hardened cement paste exhibits a power function relationship with the gel/space ratio.