A series of silver amidinate complexes has been studied both experimentally and theoretically, in order to investigate the role of the precursor complex in the control of the synthesis of silver nanoparticles via an organometallic route. The replacement of the methyl substituent of the central carbon atom of the amidinate anion by a n-butyl group allows for the crystallization of the tetranuclear silver amidinate complex 3 instead of a mixture of di- and trinuclear silver amidinate complexes 1 and 2, as obtained with a methyl substituent. The relative stabilities and dissociation schemes of various isomeric arrangements of silver atoms in 3 are investigated at the computational DFT level of calculation, depending on the substituents of the amidinate ligand. The tetranuclear silver amidinate complex 4, exhibiting a diamondlike arrangement of the four silver atoms, is also considered. Ag–N bonds and argentophilic Ag–Ag interactions are finely characterized using ELF and QTAIM topological analyses and compared over the series of the related di-, tri-, and tetranuclear silver amidinate complexes 1–4. In contrast to the Ag–N dative bonds very similar over the series, argentophilic Ag–Ag interactions of various strengths and covalence degree are characterized for complexes 1–4. This gives insight into the role of the amidinate substituents on the nuclearity and intramolecular chemical bonding of the silver amidinate precursors, required for the synthesis of dedicated AgNPs with chemically well defined surfaces.