The present study aims to compare the early stages of graphitization of the same DND source for two annealing atmospheres (primary vacuum, argon at atmospheric pressure) in an identical set-up. DND samples are finely characterized by a combination of complementary techniques (FTIR, Raman, XPS, HR-TEM) to highlight the induced modifications for temperature up to 1100 °C. The annealing atmosphere has a significant impact on the graphitization kinetics with a higher fraction of sp2-C formed under vacuum compared to argon for the same temperature. Whatever the annealing atmosphere, carbon hydrogen bonds are created at the DND surface during annealing according to FTIR. A “nano effect”, specific to the <10 nm size of DND, exalts the extreme surface chemistry in XPS analysis. According to HR-TEM images, the graphitization is limited to the first outer shell even for DND annealed at 1100 °C under vacuum.