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Cu(2)S nanowires and MnS/Cu(2)S junctions have been derived on the basis of gamma-MnS nanowires via cation-exchange reaction. Relationships between a selective cation exchange and the growth direction of the gamma-MnS nanowires are identified by means of transmission electron microscopy. In the case of gamma-MnS nanowires with [0001] growth direction, Cu(+) exchange with an initial gamma-MnS nanowire results in a Cu(2)S nanowire. In contrast, for gamma-MnS nanowires with [1-100] growth direction, Cu(+) exchange leads to a striped MnS/Cu(2)S junction. Mechanisms for this selective cation exchange are proposed. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim