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The diffusion behavior of water through epoxy coatings with micaceous iron oxide (MIO) at different pigment volume concentration (PVC) was studied by EIS techniques. Experimental results showed that, in the initial diffusion period, the diffusion processes of water through epoxy coatings immersed in 0.5 M sodium chloride (NaCl) solution followed Fick's second law. The diffusion coefficients of water through the coatings were also calculated. Within the PVC values that were studied, the diffusion coefficients of water through epoxy coatings decreased with increasing PVC, indicating that the barrier property of the pigment was the main factor affecting the water diffusion behavior.