This study demonstrates the details on the twinned structure and growth process of V-shaped silver nanowires with different bending angles (e.g., 90?, 120?, and 135?) confirmed by high-resolution transmission electron microscopy (HRTEM). These nanowires could be synthesized by a facile but effective polyol-thermal reaction method in autoclaves (160-180 ?C). The nearly uniform-size silver nanowires show an average diameter of 45 nm and length up to tens of micrometers. The microstructure and optical properties of the silver nanowires were characterized by various advanced techniques, including TEM, HRTEM, scanning electron microscopy (SEM), and ultraviolet-visible (UV-vis) spectroscopy. The twinned structure can occur in both silver spherical particles and nanowires, confirmed by HRTEM analysis and also simulated by molecular dynamics methods. The growth of V-shaped nanowires by two possible means was particularly investigated: (i) crystal lattice match-induced end-to-end or end-to-side fusion of two nanowires, and (ii) twinned crystal plane-induced growth. Such structural and mechanistic understanding of silver crystals would be useful for the shape, size, and property control of functional nanoparticles.