Texture evolution in Si/SiC multilayers deposited by atmospheric pressure chemical vapor deposition on carbonized Si(001) substrates was investigated using x-ray diffraction and transmission electron microscopy. SiC layers were epitaxial and (001)-oriented. Si layers deposited on the SiC exhibited a columnar structure with predominantly (110) orientation which could be related to the nucleation. Orientational relationships were Si[111] ║ SiC[110] and Si[112] ║ SiC[110]. Also, a low density of (112)-oriented columns was present. Extensive twinning on the vertical {111} planes within the Si columns led to domains of hexagonal stacking up to 10 nm in size with the presence of 2H-Si and 4H-Si. Subsequent SiC layer growth on the (110)-oriented Si layer resulted in a (110)-oriented SiC layer if the Si layer was carbonized prior to growth.