ACM-1 is the first example of an organoarsine metal organic framework (MOF), prepared using a new pyridyl-functionalized triarylarsine ligand coordinated to Ni(II) nodes. ACM-1 has micropores that are decorated with cis-diarsine coordination pockets. Post-synthetic metalation of ACM-1 with AuCl under facile conditions studied by single-crystal X-ray diffraction reveals the installation of dimeric Au2Cl2 complexes via the formation of As Au bonds. The Au(I) dimers display exceptionally short aurophilic bonds (2.76 angstrom) induced by the rigidity of the MOF, which acts as a unique solid-state ligand.