Imido ligand is a ubiquitous motif in organometallic chemistry, serving roles spanning from ancillary ligands to reactive sites. The nature of M=N bond is highly depended on the metal centres and their d‐electron configuration, with late‐transition metal (LTM) imido complexes exhibiting contrasting features when compared to their early‐transition metal (ETM) analogues. Envisioning to uncover general electronic descriptor for the nature of imido ligands, we computationally investigate the solid‐state 15N NMR signatures of LTM imido complexes with various central metals, geometries and d‐electron counts, and compare them against these of the corresponding ETM systems. The spectroscopic signatures are mostly driven by the presence of filled, π‐symmetry orbitals in LTM imido complexes, suggesting the development of high‐lying π(M=N) and low‐lying σ/σ*(M=N) orbitals. This contrasts with what is observed for the reported ETM systems, for which high‐lying σ‐type orbitals determine the NMR signature. Noteworthily, Ni‐ and Pd‐imido complexes with d8 configurations exhibit highly asymmetric nitrogen‐15 NMR signature with extremely deshielded principal components, because of the presence of filled, high‐lying antibonding π*(M=N) orbitals, consistent with their high reactivity. The sensitive response of 15N NMR signature to the nature of metal sites further highlights that chemical shift is a useful reactivity descriptor.