A new highly active low-valent alkoxyniobium species has been developed following the reaction of Nb(OEt)5 with Grignard reagent such as i-PrMgCl or EtMgCl, with the material behaving as an efficient catalyst for cyclotrimerization reaction of isocyanates. In this reagent system, the existence of a low-valent niobium species was confirmed by the formation of the niobium–alkyne complex prepared from the Nb(OEt)5/Grignard reagent system and an alkyne. Furthermore, the hydrolysis and diallylation reactions of the niobium–alkyne complex provided further confirmation of its existence, with corresponding (Z)-alkene and diallylated products being isolated in good yields. A new highly active low-valent alkoxyniobium species has been developed following the reaction of Nb(OEt)5 with Grignard reagent such as i-PrMgCl or EtMgCl, with the material behaving as an efficient catalyst for cyclotrimerization reaction of isocyanates. Display omitted •A new highly active low-valent alkoxyniobium species has been developed.•An efficient catalyst for cyclotrimerization of isocyanates.•An efficient alternative to NbCl3(DME) in the field of organic synthesis.