First examples of coordinatively unsaturated, homoleptic azido complexes of low-valent group 14 elements are reported. A simple strategy uses low-valent precursors, ionic azide transfer reagents and bulky cations to obtain salt-like compounds containing E(N3)3(-) of Ge(II)/Sn(II) which are fully characterised, including XRD. Remarkably, these compounds are kinetically stable at r.t. and isolable in sub-gram quantities.