Mining waters are conventionally considered as waste streams rather than metal containing streams to derive value from. There exists a wide range of technologies for the removal of metals from waste streams, but selective recovery on a desired substrate material to produce high quality composite structures has not been in focus previously. In this work, the recovery of copper from actual and synthetic waste water sources containing a plethora of metals such as Fe, Zn, Cu and Al among others was investigated by electrowinning. The copper deposit was found to be compact and free from contamination, and moreover, under suitable operating conditions the recovery of copper from mining water type of waste stream was achieved with realistically low power consumption. The same technique was also investigated to deposit a novel carbon nanotube (CNT) film with copper to produce a high added value CNT-Cu composite structure directly from waste water solution.