A simple method for the synthesis of 3-arylbenzophosphole oxides under Suzuki-Miyaura coupling conditions has been presented. It employs benzophosphol-3-yl triflate starting materials which, prior to our work, had not been used for the synthesis of 3-arylbenzophosphole oxides. The reactions proceed over 24 h and provide a library of 3-arylbenzophosphole oxides. The synthetic access to the benzophosphol-3-yl triflates has been improved. The preliminary photophysical properties of some 3-arylbenzophosphole oxides have been investigated by absorption and emission measurements. The theoretical calculations were performed to establish structure-property relationships.