Novel mixed amido/imido/guanidinato complexes of niobium are reported. The complexes were synthesized by insertion of two equivalents of di-isopropylcarbodiimide (i-Pr-cdi) or bis-cyclohexylcarbodiimide (Cy-cdi) respectively, into the niobium–amido bonds of [Nb(NR₂)₃(N-t-Bu)] (1, R = Me; 2, R = Et) starting out from [NbCl₃(N-t-Bu)(py)₂] and the respective LiNR₂ reagent (py = pyridine). Four representative examples of these mixed ligand amido/imido/guanidinato compounds were synthesized and were characterized by ¹H-NMR, ¹³C-NMR, ¹⁵N-NMR, CHN-analysis, mass spectrometry and infra-red spectroscopy. The molecular structures of [Nb(NR₂){η²-(i-Pr-N)₂C(NR₂)}₂(N-t-Bu)] (3, R = Me; 4, R = Et) in the solid state were determined by single-crystal X-ray diffraction studies and are discussed together with the molecular structure of the starting compound [Nb(NMe₂)₃(N-t-Bu)] (1). The thermal properties of the new compounds depend on the substitution at the guanidinato ligand. Complexes of i-Pr-cdi are significantly more volatile than complexes of Cy-cdi as revealed by thermogravimetric analysis. Preliminary experiments using 3 as a single-molecule source for metal–organic chemical vapour deposition (MOCVD) in the absence of ammonia indicate the formation of the stoichiometric, and surprisingly carbon-free, cubic niobium nitride phase.