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In this paper, the N,N‐dimethylformamide (DMF)‐assisted shape evolution of highly uniform and shape‐pure copper nanocrystals (Cu NCs) is presented for the first time. Colloidal Cu NCs are synthesized via the disproportionation reaction of copper (I) bromide in the presence of a non‐polar solvent mixture. It is observed that the shape of Cu NCs is systematically controlled by the addition of different...