The heteroepitaxial growth of 3C-SiC films on on-axis (100), (110), and (111) Si oriented substrates has been investigated. A multistep growth process using low-pressure chemical vapor deposition with trichlorosilane as the silicon precursor was conducted at a growth temperature of 1350 °C. X-ray diffraction analysis (θ-2θ and polar figure) and numerical simulation have been shown to be a suitable method to investigate and understand the SiC film structural properties for each substrate orientation. Epitaxial SiC films with first order twins, at least for growth on (100) and (111) Si, were obtained. SiC growth on (110) Si, on the other hand, showed a change in the growth direction by the observation of first and second order twins from the ⟨110⟩ to ⟨111⟩ direction. This is due to the high growth rate of (110) 3C-SiC/(110) Si heteroepitaxial system which encourages the SiC film to grow in a direction with a higher packing density. It was observed that the 3C-SiC surface morphology and average residual stress depends strongly on the silicon substrate orientation, as confirmed by atomic force microscopy analysis and radius of curvature measurements.