In this study, silicon coating was deposited on melt-infiltrated SiC composites using atmospheric plasma spraying and then annealed at 1100 and 1250 °C for 1–10 h to investigate the effect of annealing on the layer. The microstructure and mechanical properties were evaluated using scanning electron microscopy, X-ray diffractometry, transmission electron microscopy, nano-indentation, and bond strength tests. A silicon layer with a homogeneous polycrystalline cubic structure was obtained without phase transition after annealing. After annealing, three features were observed at the interface, namely β-SiC/nano-oxide film/Si, Si-rich SiC/Si, and residual Si/nano-oxide film/Si. The nano-oxide film thickness was ≤100 nm and was well combined with SiC and silicon. Additionally, a good bond was formed between the silicon-rich SiC and silicon layer, resulting in a significant bond strength improvement from 11 to >30 MPa.