An [n×1] head‐to‐tail bonding strategy has been used for the synthesis of ReI metallacycles. From a k3N‐dicarbonyl precursor, a single discrete [4×1] square assembly was isolated and characterized, whereas a k2N‐tricarbonyl precursor led to two major species, a square and a [3×1] triangular assembly. Solid‐state X‐ray diffraction study has confirmed the high angular distortion (71° to 96°) of the k2N precursors. The electrochemical reversibility of the triangular (5) and square (6, 7) assemblies is increased with respect to that of their precursors. Photophysical investigation has confirmed pronounced red‐shifts in the emissions of the k3N‐dicarbonyl species 4 (935 nm) and 7 (980 nm), as confirmed by density functional theory (DFT) and time‐dependent DFT (TD‐DFT) calculations.