Both carbon and silicon are group IV members, but carbon has the smaller atomic number. Diamond, with the same crystalline structure as that of silicon, is expected to act as the basic material for the next generation of high-power electronic, optoelectronic, bio/chemical electronic, quantum computing devices, etc. This is because diamond exhibits electrical properties similar to those of silicon, while having superior physical properties. In this chapter, the author reviewed and discussed the homoepitaxial growth of high-quality single-crystal diamond films with atomically flat surfaces, by using plasma-enhanced chemical vapor deposition (PECVD).