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Transition-metal-catalyzed nitrene transfer is a convenient method to introduce nitrogen into simple substrates through either alkene aziridination or C–H bond amination. Silver complexes have an unusual capability to accommodate a broad range of N-donor ligands and coordination geometries in catalysts competent for nitrene transfer. This behavior has resulted in the ability to achieve tunable chemoselectivity between aziridination and C–H bond amidation, as well as tunable site-selective functionalization between two different C–H bonds. In this paper, efforts to engage the diversity of silver and rhodium catalysts to accomplish selective and tunable aziridination of mixtures of alkenes are discussed. It was found that the selectivity of dinuclear Rh catalysts is dictated largely by steric effects, while the identity of the ligand on silver can be tuned to influence whether the steric or electronic features in the competing alkenes is the primary factor controlling which precursor is preferentially aziridinated.