Metals usually have three crystal structures: face-centered cubic (fcc), body-centered cubic (bcc), and hexagonal-close packed (hcp) structures. Typically, metals exhibit only one of these structures at room temperature. Mechanical processing can cause phase transition in metals, however, metals that exhibit all the three crystal structures have rarely been approached, even when hydrostatic pressure or shock conditions are applied. Here, through in situ observation of the atomic-scale bending and tensile process of ∼5 nm-sized Ag nanowires (NWs), we show that bending is an effective method to facilitate fcc-structured Ag to access all the above-mentioned structures. The process of transitioning the fcc structure into a bcc structure, then into an hcp structure, and finally into a re-oriented fcc structure under bending has been witnessed in its entirety. This re-oriented fcc structure is twin-related to the matrix, which leads to twin nucleation without the need for partial dislocation activities. The results of this study advance our understanding of the deformation mechanism of small-sized fcc metals.