In this work, we were able to control the preferred growth orientation of 3C-SiC by using either methane (CH4) or toluene (C7H8) as the carbon precursor in a SiCl4-based SiC CVD. At T ≤ 1250 ℃ and p = 10 kPa, the resulting 3C-SiC coatings were highly <111>-oriented in the C7H8 process, whereas they were almost randomly oriented in the CH4 process. At T > 1250 ℃ both processes resulted in highly <110>-oriented 3C-SiC coatings. By considering C6H6 and CH3 the main active carbon-containing film forming species, their adsorption behaviors on 3C-SiC (111) and (110) planes were shown via quantum chemical calculation to be significantly different: