Sustainable recovery of tellurium (Te) from large-scale wastewater is of great importance to offer stable supply of this strategic element. However, the concentration of tellurium is very low, and there is usually coexisting metallic ion of copper. In this study, a novel selective and efficient electrochemical extraction of Te and Cu from HCl solutions was first reported with stainless steel electrode. The interfacial growth behavior of electrodeposition was measured by the emerging in situ synchrotron radiation dynamic X-ray images. A turbulent reactor was employed for the stepwise electrodeposition, and nanometric powder was produced owing to the largely improved mass transport. High-purity 93.2% tellurium and 98.3% copper were selectively and efficiently recovered with the current efficiency of similar to 85% and extraction ratio of similar to 95%. This mass transport assisted method may be explored as a promising solution to overcome the limitation of present metal recycling and water purification.