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A cold bias of ~-2 K was found for Channel 6 (13.3 μm) of the Imager instrument on the 13th of Geostationary Operational Environmental Satellite (GOES-13) during its postlaunch tests. Similar bias was found previously for GOES-12 and for other instruments (the High Resolution Infrared Radiation Sounder, the Moderate Resolution Imaging Spectroradiometer, and the Spinning Enhanced Visible and Infrared Imager) in the similar spectral region. It was often suspected that the spectral response function (SRF) of these instruments may be in error; in some cases, it had been demonstrated that an altered SRF can eliminate most of the differences between the measured and the expected values. Using products recently developed for the Global Space-based Inter-Calibration System, this paper concluded that an SRF error is the root cause for the GOES Imager Channel 6 bias. Based on this theory, an algorithm was developed to correct for the bias. Application of this correction to GOES-13 Imager Channel 6 resulted in an SRF shift of -2.1 cm-1. The remaining biases have mean of nearly zero and much reduced standard deviation and are independent of the thermal structure of the interlaying atmosphere. This correction has also been successfully applied of other channels and of other GOES, which was described in a companion paper.