AbstractDetritiation facilities produce low activity tritiated water from which tritium cannot be recovered. Bipolar electrolysis, based on the electrochemical permeation of hydrogen and its isotopes through Pd–Ag alloy membranes, allows tritiated water enrichment together with negligible gaseous tritium release. Our purpose is to enrich water from 500 Ci/l (1.85×1013 Bq/l) to more than 2000 Ci/l (7.40×1013 Bq/l). We first describe the principle of bipolar electrolysis and its application to isotopic enrichment. The experimental part of this work consists of the determination of the isotopic separation factors. From these experimental values, we simulated the working of an operational cell and we demonstrate the feasibility of the process.