Well-defined surface-enhanced Raman scattering (SERS) active systems were fabricated by single-crystalline noble metal nanowires. Crossed and parallel nanowire pairs were constructed by using a nanomanipulator to create SERS hot spots in the form of nanowire junction. SERS spectra of brilliant cresyl blue (BCB), p-mercaptoaniline (pMA), and p-mercaptobenzoic acid (pMBA) were observed at the junction of two nanowires. The SERS enhancement and polarization dependence are correlated well with the enhanced electric field intensities calculated by the finite difference time domain (FDTD) method for specific nanowire geometries. These simple and effective SERS active systems have a practical advantage that the hot spots can be readily located and visualized by an optical microscope. These well-defined SERS active systems based on noble metal nanowires can be further developed to find applications in a variety of biological and chemical sensing.