Reaction of N-bromohexamethyl disilazane (Me 3 Si) 2 NBr with substituted triorganyl silanes R 1 R 2 R 3 SiH results in asymmetric disilazanes Me 3 SiNHSiR 1 R 2 R 3 and bromination product, bromotrimethyl silane Me 3 SiBr. The reaction has demonstrated an unusual dependence on specific solvation. In benzene, bromination occurs immediately after mixing of the reagents, while in cyclohexane, the reaction products are formed only under UV-irradiation. Application of photoinduced CIDNP method has shown that the mechanism of bromination of triorganyl silanes is comprised of a series of consecutive radical stages involving N-centered disilazanyl (Me 3 Si) 2 N and Si-centered silyl R 1 R 2 R 3 Si radicals.