In this work we show, using the example of a series of [Cu(Xantphos)(NˆN)]⁺ complexes (NˆN being substituted 5-phenyl-bipyridine) with different peripheral NˆN ligands, that substituents distant from the main action zone can have a significant effect on the physicochemical properties of the system. By using the C≡C bond on the periphery of the coordination environment, three hybrid molecular systems with −Si(CH₃)₃, −Au(PR₃), and −C₂HN₃ (CH₂)C₁₀H₇ fragments were produced. The Cu(I) complexes thus obtained demonstrate complicated emission behaviour, which was investigated by spectroscopic, electrochemical, and computational methods in order to understand the mechanism of energy transfer. It was found that the −Si(CH₃)₃ fragment connected to the peripheral C≡C bond changes luminescence to long-lived intra-ligand phosphorescence, in contrast to MLCT phosphorescence or TADF. The obtained results can be used for the design of new materials based on Cu(I) complexes with controlled optoelectronic properties on the molecular level, as well as for the production of hybrid systems.