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The present invention relates to a novel catalytic system for polymerisation and, specifically, for preparing conjugated diene polymers with a polar function at the chain end. Said catalytic system is made up of a metal salt of a rare earth metal and, as an alkylating agent, an organometallic compound based on a metal from the second or thirteenth column of the periodic table, capable of transferring a polar function to the diene elastomer during the conjugated diene polymerisation step. The novel catalytic system reduces the steps required for synthesising a functional diene elastomer at the chain end, while guaranteeing optimal functionalisation, advantageously near or equal to 100%.