Ultrathin metallic silicide nanowires with extremely high aspect ratios can be easily grown, e.g., by deposition of rare earth elements on semiconducting surfaces. These wires play a pivotal role in fundamental research and open intriguing perspectives for CMOS applications. However, the electronic properties of these one-dimensional systems are extremely sensitive to atomic-sized defects, which easily alter the transport characteristics. In this study, we characterized comprehensively TbSi2 wires grown on Si(100) and correlated details of the atomic structure with their electrical resistivities. Scanning tunneling microscopy (STM) as well as all transport experiments were performed in situ using a four-tip STM system. The measurements are complemented by local spectroscopy and density functional theory revealing that the silicide wires are electronically decoupled from the Si template. On the basis of a quasiclassical transport model, the size effect found for the resistivity is quantitatively explained in terms of bulk and surface transport channels considering details of atomic-scale roughness. Regarding future applications the full wealth of these robust nanostructures will emerge only if wires with truly atomically sharp interfaces can be reliably grown. © 2016 American Physical Society.