Glancing angle deposition (GLAD) has been developed into a powerful means to prepare noble metal nanostructures as substrate for surface-enhanced Raman scattering (SERS), which exhibited potential applications for trace level detections of chemicals. Due to their characteristic properties of localized surface plasmon resonance (LSPR), Ag nanostructures are the mostly recognized ones for SERS applications, which, however, are facing several problems, e.g., low melting point, easily be oxidized and sulfured, and low chemical stability, etc. Although metal oxides coating has been proven an effective way to solve these problems but at a cost of the SERS sensitivity. Thus, alloying Ag into binary alloy nanostructures could be an alternative way.We report in this study that by GLAD using two e-beams simultaneously, we could produce Ag-based binary alloy nanostructures with arbitrary composition. The alloy nanostructures, if Ag-rich, were in the form of Ag-based solid solutions. Due to the addition of the second element, the Ag-based alloy nanostructures (Ag-Ti, Ag-Al, etc.) exhibited better performance of LSPR with tunable resonance wavelength, good thermal stability, chemical stability and temporal stability, and strengthened the adhesion of the nanostructures on the silicon substrate. This makes these alloy nanostructures promising SERS substrate for real detection applications.Deposition of mixed nanostructures of Ag with metal oxides was also achieved by the dual e-beam GLAD method.