Au nanowires (AuNWs) were produced by electroless reduction of HAuCl4 in a micellar structure formed by oleylamine and investigated by means of high-resolution transmission electron microscopy (HRTEM). Micrometer long ultra-thin flexible AuNWs with 1—2 nm diameter and AuNWs with about 12 nm diameter and a few hundred nm length were produced. Their extremities show a characteristic bulging. In contradiction with previous work, the bodies of the 12 nm nanowires are defect-free along the axial direction, their extremities, however, show the presence of twin boundaries. Ultra-thin AuNWs were often found as bundles presenting lengths of few micrometers. Although they are stable in solution for months, they were found to be quite sensitive to electron beam irradiation during HRTEM experiments, with a tendency to break up into face centered cubic (fcc) Au droplets. It is proposed that the micellar configuration of oleylamine plays a fundamental role in the atomic arrangement of nanowires. Finally, we anticipate our results to be a starting point for a more realistic experimental investigation of surface effects on the mechanical properties of ultra-thin nanowires with high aspect ratio, which have been only widely exploited theoretically.