Three series new NH2-benzophosphole oxides were synthesized from cycloaddition of o-aminophenyl phosphine oxide with alkynes. The relationship between the location of the amino group and the photophysical properties were studied by absorption and emission spectroscopies and theoretical calculation. 4-NH2-benzophosphole oxides show strong fluorescence emission and high fluorescence quantum efficiency. This "One stone three birds" process provides rapid access to multiple organophosphorus-based luminogens for the structure-property relationship study.