One century ago, Camillo Golgi described 'perineuronal nets' enwrapping the cell bodies and proximal dendrites of certain neurons in the adult mammalian central nervous system and suggested that they represent a supportive and protective scaffolding. Although other neuroanatomists validated the existence of these nets on selected neurons in the adult brain, there was a lack of agreement on their origins, composition and function. The application of modern molecular and ultrastructural methods has brought new insights and a renewed interest in these classic observations. Recent data suggest that perineuronal nets result from the visualization of extracellular matrix molecules that are confined to the space interposed between glial processes and the nerve cells that they outline. The material confined to these spaces can be visualized selectively by antibodies directed to glycoproteins (e.g., tenascin and restrictin/janusin), proteoglycans (e.g., chondroitin sulfates), markers for hyaluronan as well as by lectins recognizing N-acetylgalactosamine and by monoclonal antibodies directed to epitopes on unknown molecules (e.g., HNK-1, VC1.1 and Cat 301). This review examines the emerging clarification of classical observations of perineuronal nets and the functional implications suggested by their molecular composition. Also discussed are studies that further extend observations on the time of development and of the specificity in the occurrence of perineuronal nets. In the adult brain the molecules constituting the 'perineuronal nets of matrix' could serve as recognition molecules between certain neurons and their surrounding cells and participate in the selection and consolidation of their relationship.