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This letter is focused on the microwave signature characterization of the Greenland ice sheet. Such characterization is carried out by exploiting the S- and Ku-band brightness temperatures measured by the radar altimeter RA-2 when it operates as a radiometer during the ENVISAT Commissioning Phase for the purpose of calibrating the receiver. Despite the poor radiometric resolution and the calibration issues, this activity represented a unique opportunity to gather brightness temperatures at frequencies that are not available from current spaceborne microwave radiometers. The analysis of the passive RA-2 data investigates the influence of terrain height and of the temperature of the snow layers on the brightness temperatures at RA-2 bands. The effect of the different penetration depths of the electromagnetic radiation at S- and Ku-bands is also pointed out. Measurements from the Advanced Microwave Scanning Radiometer for the Earth Observing System are used to complement the data provided by RA-2 and to verify their reliability.