A novel method to perform small-scale laboratory experiments that reproduce concrete–bentonite and concrete–groundwater interactions has been developed. Such interfaces will prevail in engineered barrier systems used for isolation of nuclear waste. With the goal of optimizing the experimental method, this work has analysed the geochemical interaction of distilled water, low-pH cement mortar and FEBEX-bentonite for 75 days. Limited but evident reactivity between the materials was observed, mainly decalcification in cement mortar, carbonation at the interface with bentonite and Mg enrichment in bentonite. These results are consistent with the state-of-the-art literature and were used to validate this small-scale pilot laboratory experiment to establish the basis for further studies comparing the behaviour of different buffer and cement materials.