Aromatic organosilanes bearing C(sp 2)-Si bonds have found increasing applications across the chemical science, yet are mostly produced by atom-uneconomical stoichiometric procedures. Catalytic alternatives using hydrosilanes as silicon sources have also been described but they display unfavorable thermodynamics and are mostly based on expensive catalytic systems, often derived from noble metals, or lack generality. Herein, we describe the use of an alternative silicon source, namely the tert-butyl-substituted silyldiazenes (tBu-N=N-SiR3), that are readily accessible from commercially available precursors and whose structure enables the C(sp 2)-H bond silylation of unactivated heteroaryl and aryl compounds under ambient, transition-metal free catalytic conditions.