With the accelerated development of surface well cementing technology, the engineering site has higher requirements for the early fluidity and coagulation performance of surface well cementing water slurry. In order to improve the top-off efficiency of cement injection operation in cementing engineering and improve the application of cementing engineering field operation, the method of nanoalumina particles modified cementing cement was proposed, and the NMR technique was used to study the change characteristics of the hydration reaction of nanoalumina-modified cement slurries (with the water-cement ratio of 0.44) with the mass fractions of 0.00% wt, 0.05% wt, 0.10% wt, 0.15% wt, and 0.20% wt at different hydration ages were investigated to characterize the changes in hydration reactions, and to probe the aqueous phase distribution, changes in the total signal amount of physically bound water, peak shape index, and migration rate of the nanoalumina-modified cements. The results showed that the T2 patterns of nano-alumina-modified cement pastes at the hydration stage would show three relaxation peaks, corresponding to the flocculated structure-filled water (0.1−10 ms), capillary water (10 ms), and free water (800−1000 ms), respectively; and the total signal of the physically bound water decreased gradually with the increase of the mass fraction of nanoalumina, in which the nanoalumina-modified cement pastes with the mass fraction of 0.20%wt. Alumina-modified cement paste has the fastest reduction rate of signal; the peak shape index shows the trend of increasing and then decreasing, when the hydration reaction is carried out to 600 min, the modified cement paste with mass fraction of 0.20%wt has the fastest rate of change, and the rate of the relaxation peak moving to the short relaxation direction is accelerated; the combination of the migration rate of the nanoalumina-modified cementing cement hydration reaction stage division, and the hydration mechanism of its hydration mechanism respectively acted in the four Hydration period: ① initial hydration period (5−60 min), the hydration rate did not change significantly; ② accelerated hydration period (60−600 min), nano-alumina to make the physical binding water in the cement paste into chemical binding water in a shorter period of time, the hydration process is accelerated to achieve the effect of promoting the hydration of the cement; ③ stabilized hydration period (600−1200 min), the cement system tends to stabilize; ④ Delayed hydration period (1200−1800 min), the rate of conversion of physically bonded water to chemically bonded water slows down, and the hydration process of cement slows down. It was concluded that the hydration period of nanoalumina-modified cement paste can be divided into four stages, and nanoalumina plays the roles of physical filling, accelerating, stabilizing, and retarding for the cement paste, respectively. In the accelerating period, nanoalumina promotes the early flow of cement, which is conducive to the pumping and flow of cement paste, and in the retarding period, nanoalumina retards the further hydration process of cement, which is conducive to the development of early strength. Among them, the nano-alumina modified cement paste with a mass fraction of 0.20% wt has the greatest influence on the cement hydration process, promotes the conversion of filler water to bound water, and accelerates the hydration reaction of cement paste to the greatest extent during the accelerated hydration period, which serves as the basis for providing guidance for the preparation and application of cementing cements in the field.