The combination of VCl3(THF)(3) and N,N-bis(trimethylsilyl)aniline (1a) is an efficient catalyst for the [2+2+1] coupling reaction of alkynes and azobenzenes, giving multisubstituted pyrroles. A plausible reaction mechanism involves the generation of a mono(imido)vanadium(III) species as an initiation step, where la served as an imido source with concomitant release of 2 equiv of ClSiMe3, followed by a reaction with azobenzene to form a catalytically active bis(imido)vanadium(V) species via N=N bond cleavage.