The single crystals of 9-phenyl-9-dibenzophosphole chalcogenides {oxide (1), sulfide (2) and selenide (3)} and a mixed crystal of 2 and 3 have been prepared and characterized by X-ray diffraction analysis. Several intermolecular interactions such as p-p and Se-H were observed in the mixed crystal of 2 and 3. The mixed crystal of 2 and 3 exhibited enhanced phosphorescence compared to the pure constituent crystal (2 or 3) at low temperature.