Luminescent complexes with arsane ligands have garnered considerable interest due to their uncomplicated structure and effective luminescence. Particularly, rigid monodentate arsane ligands, wherein the substituents of the arsenic atom are bridged, have proven advantageous in enhancing emission intensity. In this study, we synthesized non‐bridged, O‐bridged, S‐bridged, and O,O‐bridged triphenylarsine derivatives using the safe and efficient protocols developed in our previous work. We then created platinum dihalide (PtX2, X = Cl, Br, I) complexes with these arsane ligands. Their structures were determined through single‐crystal X‐ray diffraction, revealing significant influences on geometry by the counter anion and the arsane/phosphane ligand. Additionally, we elucidated the correlation between the ligand structure and the solid‐state emission properties.