The range between satellite and surface target was acquired by processing the weak received waveform which was transmitted from the space-borne laser altimeter and reflected by earth surface. Combined with the precise orbit and attitude data, the accurate location and elevation of laser footprint were calculated. As for the altimeter with elevation accuracy of 10 cm magnitude, the systematic error on attitude angles influencing the accuracy severely should be calibrated effectively. The analytic model of attitude angle error associated with priori knowledge of earth surface was deduced, and the calibration method used to eliminate the attitude error was designed, which utilized the ocean surface as calibration field, was by way of satellite attitude maneuver and based on least squares estimation algorithm. The results of simulation show that the designed method can estimate the systematic error precisely and effectively, even if the mass observed data were lost, the estimated bias is less than 5%. This on-orbit calibration method is beneficial to the systematic error correction for the space-borne laser altimeter, and is of reference significance.