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The first example of a triply bridging (μ 3 -P) phosphine ligand has been discovered in the crown-shaped [Cu 3 (μ 2 -Hal) 3 L] (Hal=Cl, Br, or I) complexes supported by tris[2-(2-pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ 3 -P-bridging pattern, revealing the interaction of the same lone pair of phosphorus with three valence 4s-orbitals of Cu atoms. The presented complexes exhibit outstanding blue phosphorescence (λ em =442-465 nm) with the quantum efficiency reaching 100 %. The complex [Cu 3 (μ 2 -I) 3 L] also exhibits remarkable thermo- and mechanochromic luminescence resulting in a sharp change in the emission colour upon external stimuli. These findings essentially contribute to coordination chemistry of the pnictine ligands., (© 2021 Wiley-VCH GmbH.)