In this study, we used near-infrared spectroscopy to measure the moisture penetration in epoxy adhesives and investigated the difference in the diffusion coefficients between the bulk and the adhesive layer. Moisture diffusion was evaluated under 100% RH and water immersion conditions. First, the effects of the curing agents and additives on moisture diffusion in the bulk were gravimetrically evaluated using epoxy-coated quartz glass plates. Different diffusion behaviors were observed depending on the curing agent used. The presence of additives resulted in higher diffusion coefficients, whereas the overall moisture content was low. Next, the moisture distribution in the adhesive layer was visualized using a specimen sandwiched between the quartz glass plates, and the diffusion coefficient of the adhesive layer was calculated. The diffusion coefficient in the adhesive layer was larger than that in the bulk. For adhesives cured with hydrophobic diamine, the diffusion coefficient within the adhesive layer increased by approximately 1.5 times compared with that in the bulk, regardless of the exposure environment. The adhesive, composed of a resin, Dicyandiamide, and additives, showed a 2-fold increase in the diffusion coefficient under high-humidity exposure conditions but no significant change under the water immersion condition. Therefore, these results suggest that, for an accurate analysis of moisture distribution, it is important to measure the diffusion coefficient of the adhesive layer directly rather than using the diffusion coefficient of the material itself.