Not for tools. The MesoAmerican Indians worked with silver, gold and occasionally natural copper because it was maleable -- but only for adornment and ornamentation. Tools and weapons were made of wood, stone or obsidian, or occasional odd materials such as sharks' teeth or sawfish snouts.
I guess its just a matter of semantics, for me the knowledge of metallurgy defines the age - whether it was used for tool making by the populace as a whole or not doesn't mean as much to me because the technology existed. When we talk about the early human and pre-human people, the understanding of metallurgy hadn't existed yet.
The Eskimo use meteoric iron.