Several examples of the cyaphide‐azide 1,3‐dipolar cycloaddition reaction to afford metallo‐triazaphospholes are reported. The gold(I) triazaphospholes Au(IDipp)(CPN3R) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene; R=tBu, Ad, Dipp), magnesium(II) triazaphospholes, {Mg(DippNacNac)(CPN3R)}2 (DippNacNac=CH{C(CH3)N(Dipp)}2, Dipp=2,6‐diisopropylphenyl; R=tBu, Bn), and germanium(II) triazaphosphole Ge(DippNacNac)‐(CPN3tBu) can be prepared straightforwardly, under mild conditions and in good yields, in a manner reminiscent of the classic alkyne‐azide click reaction (albeit without a catalyst). This reactivity can be extended to compounds with two azide functional groups such as 1,3‐diazidobenzene. It is shown that the resulting metallo‐triazaphospholes can be used as precursors to carbon‐functionalized species, including protio‐ and iodo‐triazaphospholes.