Arsenic ligands have attracted considerable attention in coordination chemistry. Arsenic(III) halides are the most important starting materials in the preparation of monodentate arsenic ligands. In this work, we optimized the synthetic methodologies of arsenic(III) halides (AsX3; X = Br, I) and examined the difference of their physical properties such as solubility to organic solvent and reactivity to nucleophiles. In addition, a wide variety of monodentate arsenic ligands were prepared with the obtained AsX3. Finally, the obtained monodentate arsenic ligands were utilized for copper-free Sonogashira cross-coupling reaction in the reaction system with porphyrin. The results showed that monodentate arsenic ligands have higher catalytic activity compared with triphenylphosphine because of the difference of the electronic features of lone pairs between arsenic and phosphorus atoms.