The tricarbonylrhenium complexes that incorporate a mesoionic carbene ligand represent an emerging and promising class of molecules, the solid-state optical properties of which have rarely been investigated. The aim of this comprehensive study is to compare three of these complexes with their 1,2,3-triazole-based analogues. The Hirshfeld surface analysis of the crystallographic data revealed that the triazolylidene derivatives are more prone to π–π interactions than their 1,2,3-triazole-based counterparts. The FT-IR and electrochemical data indicated a stronger electron donor effect from the organic ligand to the rhenium atom for triazolylidene derivatives, which was confirmed by DFT calculations. All compounds were phosphorescent in solution, where the 1,2,3-triazole-based complexes showed unusually strong dependence on dissolved oxygen. All compounds also emitted in the solid state, some of them exhibited marked solid-state luminescence enhancement (SLE) effect. The 1,2,3-triazole based complex Re-Phe even displayed astounding photoluminescence efficiency with quantum yield up to 0.69, and proved to be an excellent candidate for applications linked to aggregation-induced emission (AIE). Interestingly, one triazolylidene-based complex (Re-T-BOP) showed attractive antibacterial activity. This study highlights the potential of these new molecules for applications in the fields of photoluminescent and therapeutic materials, and provides the first bases for the design of efficient molecules in these research areas.