One-dimensional single crystal nanostructures have garnered much attention, from their low-dimensional physics to their technological uses, due to their unique properties and potential applications, from sensors to interconnects. There is an increasing interest in metallic titanium nanowires, yet their single crystal form has not been actualized. Vapor-liquid-solid (VLS) and template-assisted top-down methods are common means for nanowire synthesis; however, each has limitations with respect to nanowire composition and crystallinity. Here we show a simple electrochemical method to generate single crystal titanium nanowires on monocrystalline NiTi substrates. This work is a significant advance in addressing the challenge of growing single crystal titanium nanowires, which had been precluded by titanium's reactivity. Nanowires grew non-parallel to the surface and in a periodic arrangement along specific substrate directions; this behavior is attributed to a defect-driven mechanism. This synthesis technique ushers in new and rapid routes for single crystal metallic nanostructures, which have considerable implications for nanoscale electronics.