Diamond was deposited on Si(100) substrates by the microwave plasma-assisted chemical vapor deposition method in three steps: carburization, biasing, and growth. High-resolution transmission electron microscopy in cross-sectional view has been used to observe the evolution of microstructures around the interfacial region between diamond and Si in each processing step. The chemistry near the interface was characterized with elemental mapping using an energy-filtered imaging technique with electron energy loss spectroscopy. An amorphous carbon layer, β-SiC and diamond particles, and graphite plates have been observed in the carburization stage. β-SiC can form in epitaxial orientation with Si in the following stage of biasing. Graphite and amorphous carbon were not observed after the bias was applied. Diamond grains were aligned in a strongly textured condition in the growth stage. It has been found that diamond, SiC, and Si all have (111) planes in parallel. The relation of the evolution of microstructure with the processing conditions is also discussed.