The monolayer characteristics of phosphate amphiphiles with azobenzene at air/water interface were studied by the measurment of $pi-A$ curves and absorption spectra. Immediately after being spread on the water surface, these amphiphiles having strong intermolecular hydrogen bonding interactions showed the typical absorption spectra which resulted from domain formation. But the aggregated domains could be controlled by changing the subphase conditions (adding bulky salt and rasing pH). Addition of metal ions in subphase changes the molecular orientation of monolayer. As the metal ion charge increases ($1leq2$ < 3 < 4 valence), the absorption maximum (310nm) of the amphiphile with azobenzene shifts to a longer wavelength (350nm) which means that the orientation of the amphiphile is tilted. These results suggest that the molecular orientation, and furthermore the aggregation state of monolayer can be possibly controlled by the interaction of metal ions with different charge types.