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The present invention relates to a method of monitoring a geological CO2 storage site, in which the following steps are carried out : the contents of CO2 and rare gases contained in a geological aquifer lying above the cover for a future CO2 storage site are analyzed; the contents of rare gases associated with the injected CO2 are analyzed; the rocks constituting said cover are characterized; a leakage of CO2 and rare gases coming from the storage site and passing through the cover into said upper geological layer is modelled; a threshold for at least one rare-gas ratio corresponding to a CO2 leak rate is determined; a ratio of rare gases present in the geological layer lying above said storage site is measured and compared with said threshold; and the CO2 leakage rate is determined.