The chloride diffusion of marine high-performance concrete under a couple of actions, flexural load and freezing–thawing, was investigated by a fast freezing and thawing test in NaCl solution. Concrete specimens of 100 × 100 × 515 mm were tested under bending load and 300 freeze–thaw cycles under the stress levels of 15%, 30%, and 50% of the ultimate fracture modulus. The change in the microstructure of the concrete was analyzed by SEM and MIP. The results indicated that the chloride diffusion coefficient of concrete under the coupling effect of flexural load and freezing–thawing or simple flexural load increased with the increasing in the flexural stress level, and the chloride diffusion coefficient was approximately exponential to the flexural stress level, as D = 0.8777e^1.668σ for a couple of actions of flexural load and freezing–thawing, and D = 0.8336e^1.3231σ for a simple flexural load. The resistance ability of concrete to chloride diffusion was reduced by the freezing–thawing procedures, the resisted ability dropped more severely under a couple of actions of flexural load and freezing–thawing than simple flexural load at the same stress level. Micro-cracks at the interfacial transition zone between the aggregate and the paste matrix in concrete was induced under a couple of actions of flexural load and freezing–thawing, which increased the average pore size and total pore volume, resulting in the modification of the pore size distribution in the concrete. The influence of a couple of actions of flexural load and freezing–thawing on the concrete was greater than that of simple flexural load.