Grouting is the effective method to prevent water inrush and reinforce fractured surrounding rocks in the construction of the submarine tunnel. The seawater intrusion will lead to obvious changes in the rheological properties of slurries, which can be adverse for the diffusion properties of slurries. This study aimed to identify the impact of seawater intrusion on the constitutive relationship of superfine cement–sodium silicate slurry (SC-S slurry). The chemical gelling time, viscosity, and rheological model of the slurry were studied. The concentrations of seawater ranged from 0% to 100%. The water–cement ratio ranged from 0.6 to 2.0. This study revealed that seawater significantly shortened the chemical gelling time of the slurry. The effect was more pronounced as the concentration of seawater increases. Furthermore, it was observed the rheological model of SC-S slurry will change from Bingham model to Herschel–Bulkley model with the increase in concentration of seawater. Rheological parameters that vary with time were also studied. The rheological constitutive models of slurry under seawater intrusion were established.