Carbon nanotubes (CNTs) have unique thermal/electrical/mechanical properties and high aspect ratios. Growth of CNTs directly onto reactive material substrates (such as metals and carbon based foam structures, etc.) to create a micro-carbon composite layer on the surface has many advantages: possible elimination of processing steps and resistive junctions, provision of a thermally conductive transition layer between materials of varying thermal expansion coefficients, etc. Compared to growing CNTs on conventional inert substrates such as SiO2, direct growth of CNTs onto reactive substrates is significantly more challenging. Namely, control of CNT growth, structure, and morphology has proven difficult due to the diffusion of metallic catalysts into the substrate during CNT synthesis conditions. In this study, using a chemical vapor deposition method, uniform CNT layers were successfully grown on copper foil and carbon foam substrates that were pre-coated with an appropriate buffer layer such as Al2O3 or Al. SEM images indicated that growth conditions and, most notably, substrate surface pre-treatment all influence CNT growth and layer structure/morphology. The SEM images and pull-off testing results revealed that relatively strong bonding existed between the CNT layer and substrate material, and that normal interfacial adhesion (0.2‒0.5 MPa) was affected by the buffer layer thickness. Additionally, the thermal properties of the CNT/substrate structure were evaluated using a laser flash technique, which showed that the CNT layer can reduce thermal resistance when used as a thermal interface material between bonded layers.