Three-dimensional (3D) nanoarchitectures have demonstrated substantial advantages in capturing the performance of traditional electrode materials. In this regard, novel Cu@SnS core–shell nanowire array is fabricated via a rational electrochemical assembly strategy. Meanwhile it is also discovered that striking structural and compositional evolution from Cu@SnS core–shell nanowires to hybrid CuS/SnS nanotubes can be achieved by a simple tuning of reaction conditions. As a proof of concept, long-term cycling stability and remarkable rate capability are exhibited by Cu@SnS nanoelectrode in the study of its Li+ storage properties (e.g., it delivers a capacity of ∼347 mAh g−1 at 3.33C even after 80 rate-varying cycles), which verifies the effectiveness of the designed 3D configuration in tackling possible electrical/mechanical failures of the electrode during repeated Li+ uptake/release process. Moreover, because of their potential for achieving high power and energy densities on a small footprint area, the designed metal sulfide nanoelectrodes may be promisingly applied in microenergy storage devices.