C60 fullerene reacted with phosphorus at high temperatures to graphitic materials with strongly differing properties. Several spectroscopic investigations as Raman, ESR, XPS and 31P-NMR as well as TEM and ESEM have shown that the structural order of the mostly micro-crystalline materials increased with increasing reaction temperatures and decreasing phosphorus content. At suitable preparation conditions carbon nanotubes are formed, which are disordered in most cases, but partly exhibit high structural order (single-wall nanotubes), too. The prepared materials are very hard, e.g. harder than silica, intensely coloured and electrically conductive. Their hardness decreased with rising phosphorus content, and their conductivity increased with decreasing phosphorus content. © 2004 Elsevier B.V. All rights reserved.