A study was conducted to demonstrate a new spontaneous hydrosilylation reaction that induced direct carbon-silicon (C-Si) bonds using silane compounds containing a neutral Si-H x moiety. The study aimed at demonstrating that covalent bonds readily formed between triethysilane (TriES) and single-walled nanotubes (SWNT) at room temperature through a spontaneous hydrosilylation reaction in the absence of any externally provided activation-energy-lowering stimuli, such as Lewis acid catalyst or the photon or thermal energies required for conventional hydrosilylation. It also demonstrated that the hydrosilylation reaction was utilized for silencing metallic SWNTs from mixtures. The spontaneous hydrosilylation was confirmed by using atomic force microscopy (AFM)-correlated nano-Raman spectroscopy.