Polycrystalline β-SiC, with grain size up to 0.2 μm, was grown on silicon substrate by electron cyclotron resonance chemical vapor deposition (ECR-CVD) from SiH4/CH4/H2 at 178–500 °C. The nucleation process and surface structure of polycrystalline SiC were investigated via observing the film surface by atomic force microscopy (AFM). Reaction species which promote polycrystalline SiC was in-situ monitored by quadruple mass spectrum analysers during deposition process, which is crucial for the control of polycrystalline SiC growth. The microstructure of SiC films were inspected by bright-field imaging, dark-field imaging, and electron diffraction in cross-sectional transmission electron microscopy. This paper will also discuss the key parameters for the nucleation and growth of polycrystalline β-SiC at very low temperature in ECR-CVD system.