Cu is a well known heat sink material due to its high thermal conductivity. However, its coefficient of thermal expansion (CH) is high. One of the most promising solutions for reducing it is to reinforce copper with carbon nanofibres (CNF) because of their low CH. To exploit the properties of the CNFs a good dispersion of the reinforcement within the matrix must be achieved. One of the processing methods used to obtain a homogeneous CNF distribution is coating the CNF with Cu using electrochemical deposition. In this paper, the effect of the carbon structure on electroless deposition technique is studied. Different CNF have been compared: herringbone (HB), platelet (PL) and longitudinally aligned (previously heat treated) (LAHT). Herringbone and Platelet CNF were heat treated at 2750 degrees C for 30' which resulted in a structure resembling graphite with loops at the fibre surface. These loops are responsible for an enhancement of the copper coating. It is shown that the Cu coverage in electroless deposition is high for the graphene plane and poor at the edges of the plane. (C) 2010 Elsevier Ltd. All rights reserved.