In this paper, a series of experiments assessing the moisture buffer value (MBV) of four internal wall assembly samples made from hygroscopic materials was performed. A modified Nordtest protocol was used. Moisture buffer values of all the investigated wall assemblies, with varying moisture loads in the range of 50% to 80%, showed a moderate moisture buffer value (MBV: 0.5–1.0 (g·m−2·%RH−1)). The results showed that in a wall assembly where the MBV of the whole assembly is lower than the MBV of the outer layers, the moisture-buffering capacity of the inner layer is untapped. Outer layers affect inner layers by changing their moisture-buffering capacity, which in turn changes the overall performance of the whole assembly. In addition, it was observed that if the penetration depth value of the outer layer is greater than its thickness, vapour reaches into the deeper layer and wall assemblies made of layers with materials characterized by a lower value of penetration depth reach steady state more slowly. The WUFI Pro tool was used to compare the simulated and experimental results. Despite the discrepancies between these results, it offers a simplified method, helping designers make decisions about which materials to choose to improve the moisture-buffering effect.