Bis(trimethylsilyl)amine is synthesized by treatment of trimethylsilyl chloride with ammonia:
:2 (CH)SiCl + 3 NH → [(CH)Si]NH + 2 NHCl
Ammonium nitrate together with triethylamine can be used instead. This method is also useful for N isotopic enrichment of HMDS.
Alkali metal bis(trimethylsilyl)amides result from the deprotonation of bis(trimethylsilyl)amine. For example, lithium bis(trimethylsilyl)amide (LiHMDS) is prepared using n-butyllithium:
:[(CH)Si]NH + BuLi → [(CH)Si]NLi  + BuH
LiHMDS and other similar derivatives: sodium bis(trimethylsilyl)amide (NaHMDS) and potassium bis(trimethylsilyl)amide (KHMDS) are used as a non-nucleophilic bases in synthetic organic chemistry.