Tungsten nitrido amido guanidinato complexes of the type WN(NR2)[(NR′)2C(NR2)]2 (R = Me, Et; R′ = iPr, Cy) were synthesized as precursors for aerosol‐assisted chemical vapor deposition (AACVD) of WNxCy thin films. The reaction of tungsten nitrido amido complexes of the type WN(NR2)3 (R = Me, Et) with two equivalents of a carbodiimide R′N=C=NR′ (R′ = iPr, Cy) resulted in two insertions of a carbodiimide into W–N(amido) bonds, affording bis(guanidinato) amido nitrido tungsten complexes. These compounds were characterized by 14N NMR, indicating distinctive chemical shifts for each type of N‐bound ligand. Crystallographic structure determination of WN(NMe2)[(NiPr)2C(NMe2)]2 showed the guanidinato ligands to be non‐equivalent. The complex WN(NMe2)[(NiPr)2C(NMe2)]2 was demonstrated to serve as a precursor for AACVD of WNxCy thin films, resulting in featureless, X‐ray amorphous thin films for growth temperatures 200–400 °C.