Bimetallic nanomaterials have attracted much attention from various fields such as catalysis, optics, magnetism, and so forth. The functionality of such particles is influenced very much by the intermetallic interactions than their individual contribution. However, compared with the synthesis of monometallic nanoparticles, the reaction parameters that need to be controlled for tuning the size, shape, composition, and crystal structure of bimetallic nanoparticles becomes challenging. This study focuses on synthesizing of bimetallic nanostructures using the alcohol reduction method, where the control over the reducing power is conceivable by varying the combination of the alcohol type, complexing agent, and metal salts. Consequently, various Cu−Co nanostructures such as Cu−Co core−shell (size ranged between 40 and 15 nm) and hollow alloy nanoparticles and nanotubes were successfully synthesized by incorporating diffusion and etching phenomena during the reduction reaction. Moreover, time-resolved sampling revealed that the formation of a Cu−Co alloy hollow nanostructure has been realized by the diffusion of the Cu core into the Co shell by controlling the reduction time gap between Cu and Co and the crystal structure besides the reduction sequences. It should be noted that the synthesis of a high-temperature (∼1300 °C) Cu−Co alloy phase was carried out at 170 °C. Among the Cu−Co alloy nanostructures, Cu−Co hollow alloy nanoparticles exhibited enhanced catalytic activity compared to metallic Cu and other Cu−Co nanostructures from the degradation reaction of methylene blue. The enhanced catalytic performance was considered to be mainly due to the alloy structure.