The surface photovoltage dopant concentration measurement of a semiconductor wafer is calibrated by biasing the semiconductor wafer into an avalanche breakdown condition in a surface depletion region; determining a contact potential difference value corresponding to an avalanche breakdown; determining small signal ac-surface photovoltage value corresponding to an avalanche breakdown; and using the values of the contact potential and the surface photovoltage to calculate a calibration constant that relates depletion layer capacitance and an inverse of the surface photovoltage.