This paper describes the growth and characterisation of Si/SiC heterojunction structures. Heterojunction structures are of interest for low on-resistance diodes and as potential solutions to fabricating SiC MOS devices with lower interface state densities. The formation of the Si/SiC heterojunction using Chemical Vapour Deposition (CVD), Molecular Beam Epitaxy (MBE), Electron Beam Evaporation under UHV conditions (EBE-UHV) and Layer Transfer (LT) are reported. The physical nature of Si/SiC structures has been investigated using scanning electron microscopy (SEM). Results of electrical characterisation of the Si/SiC heterojunctions, are also reported. Finally, thermal oxidation of a Si / SiC heterojunction structures has been performed. The C(V) characteristics of the resulting oxides are compared to conventional thermal oxides on SiC.