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A search for the B-s(0) -> D*(+/-) D--/+ decay is performed using proton-proton collision data at centre-of-mass energies of 7, 8 and 13TeV collected by the LHCb experiment, corresponding to an integrated luminosity of 9 fb(-1). The decay is observed with a high significance and its branching fraction relative to the B-0 -> D*(+/-) D--/+ decay is measured to be