Triazole-based phosphanes have recently been shown to be interesting ligands in organometallic catalysis. The synthesis of novel [2.2]paracyclophane-substituted triazole-based phosphane ligands was achieved. The possibility to synthesize these molecules in a highly enantioenriched form is also reported. Moreover, the ability of the novel ligands to coordinate with metal centers was explored. Besides a dinuclear copper complex, a PdII complex could also be isolated, the structure of which was characterized by X-ray analysis. PdII complexes derived from these ligands provide highly active catalysts for the Suzuki–Miyaura coupling of aryl chlorides.