Three groups of free‐standing chemical vapor deposition (CVD) diamond films formed with variations in substrate temperature, methane concentration, and film thickness are analyzed using high‐resolution electron back‐scattering diffraction. Primarily {001}, {110}, and {111} fiber textures are observed. In addition, corresponding primary and higher order twinning components are found. As interfaces, high angle, low angle, primary twin, and secondary twin boundaries are observed. A growth and a twinning model are proposed based on the sp3 hybridization of the bond in the CH4 molecule that is used as the deposition medium.