The compressive strength and water absorption of cement mortars with different water-binder ratio (0.35, 0.45 and 0.55) and fly ash content (0, 10%, 20% and 30%) under water immersion were investigated, and the correlation between them was further analyzed. The internal microstructure and phase composition of mortar was studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that the inside of mortar mixed with fly ash displayed the loose and porous microstructure. Therefore, the incorporation of fly ash reduced the compressive strength of mortar, especially the early strength, and the strength decreased with the increase of fly ash content, and the water absorption of mortar also increased. There was a linear correlation between the compressive strength and water absorption of mortar with the equation: fc = -3.838β + 62.332, where fc and β represented the compressive strength and water absorption, respectively. Therefore, when the water absorption of mortar immersed in water was measured, its corresponding compressive strength could be preliminarily inferred through this equation, which was of great significance for detecting and identifying the stability and safety of hydraulic structures.