Heteroepitaxial diamond has been successfully deposited on a Si(110) substrate by the microwave plasma chemical vapor deposition method. The pretreatment consisted of carburization and bias-enhanced nucleation steps. Cross-sectional transmission electron microscopy reveals that diamond can be in the cube-on-cube epitaxial relationship with the Si substrate. Various orientation relationships between diamond and Si substrates have also been observed, depending on the location where the plasma applied. Near the center of the plasma, twins were rarely observed in cube-on-cube epitaxial regions. Away from the center of the plasma ball, Σ3 twins are seen first, and then additional Σ9 and Σ27 twins occur near the edge of the plasma. In general, defect density in the epitaxial films is less than that observed in polycrystalline ones. No interlayer could be observed between diamond and silicon. In addition, 2H-type hexagonal diamond has also been found, and is in epitaxy with the Si substrate.