In this study CdTe (111)B was grown by molecular beam epitaxy on vicinal Si(001) substrates, with a variety of substrate tilt angles (θ), and tilt directions (φ) relative to . Layer quality, and content of double-domain and microtwin defects were evaluated by double crystal rocking curve (DCRC) full width at half maximum (FWHM) and x-ray diffraction, respectively. Transmission electron microscopy (TEM) was used to study interface quality and the nature of structural defects as a function of epilayer thickness. In the present investigation, substrate preparation and growth conditions, particularly initiation conditions, are correlated with Si (001) tilt. It has been found that oxide desorption processes can depend strongly on θ, especially for larger values of θ (> 4°). Currently, we routinely produce single domain, twin-free CdTe(111)B epilayers on vicinal Si (001) substrates.