Development of new procedures in analytical chemistry is currently increasingly focussed on reducing the time, cost and energy to carry out routine analyses. The conventional Dean–Stark (CDS) distillation to determine the water content is one of the most commonly used analytical methods and uses large amounts of solvent and energy. A new microwave accelerated Dean–Stark (MADS) distillation is presented as an alternative procedure. Microwaves were applied to a mixture of toluene, Weflon stir bar and olives, and the corresponding water was collected in a Dean–Stark receiver. This procedure permits fast and efficient determination of the water content of olives. Reliability and reproducibility were evaluated using statistical analyses. Different matrices were then used with MADS and the results were compared to CDS. Water determination from olives with MADS was better than that with CDS in terms of energy saving, rapidity (10 min versus 120 min), reproducibility, and cleanliness