Tetra­(thiocyanato)­corrolato-Ag­(III) complexes presented here constitute a new class of metallo-corrole complexes. The spectroscopic properties of these complexes are quite unusual and interesting. For example, the absorption spectra of these β-substituted corrolato-Ag­(III) complexes are very different from those of the β-unsubstituted corrolato-Ag­(III) derivatives. Single-crystal XRD analysis of a representative tetra­(thiocyanato)­corrolato-Ag­(III) derivative reveals C–H···Ag interactions. The C–H···Ag interactions are rarely demonstrated in the crystal lattice of a discrete coordination/organometallic compound. Optimization of the hydrogen positions of the crystal structure discloses the geometrical parameters of the said interaction as a Ag···H distance of 2.597 Å and ∠C–H···Ag of 109.62°. The natural bond orbital analysis provides information about the donor–acceptor orbitals involved in the interactions and their interaction energies. It was observed that the σC–H orbital overlaps with the vacant d-orbital of Ag with an interaction energy of 17.93 kJ/mol. The filled d-orbital of Ag overlaps with the σ*C–H orbital with an interaction energy of 4.79 kJ/mol. The highlights of this work are that the H···Ag distance is outside of the distance range for the typical agostic interaction but fitted with the weak H-bond distance. However, the ∠C-H···Ag angle is within the range of the agostic interaction. Both crystallographic data and electronic structure calculations reveal that these kinds of intermolecular interactions in square-planar d8 Ag­(III) complexes are intermediate in nature. Thus, they cannot be categorically called either hydrogen bonding or agostic interaction.