The effects of heat treatment (heating temperature and pH) on the structures and emulsifying properties of caseins were systematically studied by spectroscopy. Heat treatment from 60 to 100 ℃ resulted in an increase in their fluorescence intensity, hydrodynamic diameter, turbidity and emulsifying activity index, but decreased the size polydispersity of caseins. In the pH range of 5.5 to 7.0, the fluorescence intensity, hydrodynamic diameter, turbidity and emulsifying properties decreased with increased heating pH, but the size polydispersity of caseins increased with increased pH. The relationship between the surface fluorescence intensity and emulsifying activity was also investigated, revealing a correlation coefficient of 0.90. These results suggested that heat treatment could be used to modify the structures and emulsifying properties of caseins by appropriately selecting heating conditions.