The heteroepitaxial growth of β-SiC has been studied by pyrolysis of polyimide Langmuir–Blodgett films on silicon substrate in the temperature range 500–1000 °C in vacuum. Thin SiC films have been grown at temperatures above 700 °C. Both the onset temperature of the SiC formation and the growth rate of the SiC films were affected by the orientation of the silicon substrates. The growth rate of the SiC films increased with temperature and was controlled by the reaction of Si with C-containing reactants. By comparison with dip-coating polyimide films, it was found that the crystallinity of the SiC layers depended on the degree of order of the molecular arrangement in the polyimide films. Highly ordered superlattice structures of polyimide LB films favored the growth of single crystal SiC films.