The number of studies published in recent years on the synthesis and characterization of copper nanomaterials is growing exponentially, as a literature search (period 1991–2007) returned more than 5000 papers and patents. Despite this great interest, only a few reviews have been issued on the synthesis and characterization of Cu(0) nanostructures, and all have dealt with specific approaches, limited periods or selected morphologies. Aimed at critically reviewing the highest number of studies on Cu NPs referenced until now, this chapter presents a selection of citations taken from more than 350 papers. All the main approaches to nanocopper are briefly described, following their historic evolution and the key aspects/findings of outstanding studies. The type of synthesis approach was chosen as guideline for the classification of the different studies, while characterization results were cited, in support of the description of specific nanomaterials and/or methods. It is intended that this chapter should be considered as a basic aid for the reader wishing to approach the ‘microcosm’ of the synthesis and characterization of nonoxidized, nonsupported copper nanomaterials, in a concise and schematic manner.