Car-Parrinello molecular dynamics simulations demonstrate that pulling a single thiolate molecule anchored on a stepped gold surface does not preferentially break the sulfur-gold chemical bond. Instead, it is found that this process leads to the formation of a monoatomic gold nanowire, followed by breaking a gold-gold bond with a rupture force of about 1.2 nN. The simulations also indicate that previous single-molecule thiolate-gold and gold-gold rupture experiments both probe the same phenomenon, namely, the breaking of a gold-gold bond within a gold nanowire.