This study investigated a mechanism for controlling the shape of Cu nanocrystals fabricated using the polyol process, which considers the thermodynamic transition from a facetted surface to a rough surface and the growth mechanisms of nanocrystals with facetted or rough surfaces. The facetted surfaces were stable at relatively low temperatures due to the low entropy of perfectly facetted surfaces. Nanocrystals fabricated using a coordinative surfactant stabilized the facetted surface at a higher temperature than those fabricated using a non-coordinative surfactant. The growth rate of the surface under a given driving force was dependent on the surface structure, i.e., facetted or rough, and the growth of a facetted surface was a thermally activated process. Surface twins decreased the activation energy for growth of the facetted surface and resulted in rod- or wire-shaped nanocrystals