In this study, diamond films have been synthesized on adamantane-coated (100) Si substrates at 530 C by microwave plasma chemical vapor deposition from a gaseous mixture of methane and hydrogen. Scanning electron microscopy, Raman spectroscopy, and X-ray diffraction were employed to characterize the carbon chemical species on the Si substrate from adamantane into diamond. These measurements provide definitive evidence for formation of high-crystalline diamond film on Si substrate without any other pretreatments. Moreover, the possible mechanisms for the diamond formation are presented.