Carbon nanotubes (CNTs) grown on SiC are metal-free, well-aligned, and with low structural defects. In this study, CNT formation on SiC is examined in high vacuum (10-5torr) and ultra-high vacuum (10-8torr). Multi-wall carbon nanotubes and graphitic structures are the main products on the SiC surface at 1400-1800°C in 10-5torr. Under ultra-high vacuum, the decomposition rate of SiC is much lower than in high vacuum, indicating that SiC is decomposed by oxidation reaction. Using X-ray photoelectron spectroscopy (XPS), the intensity of the O1s peak at 530.3 eV decreases with increasing take-off angle, indicating that this oxygen species exists on the walls of CNTs. The results show that oxygen with a low pressure not only oxidizes SiC, but also forms a highly thermally stable carbon-oxygen compound, and interacts with the CNTs at high temperatures.