China is planning to launch more and more optical remote-sensing satellites with high spatial resolution and multistep gains. Field calibration, the current operational method of satellite in-flight radiometric calibration, still does not have enough capacity to meet these demands. Gaofen-1 (GF-1), as the first satellite of the Chinese High-resolution Earth Observation System, has been specially arranged to obtain 22 images over clean ocean areas using the Wide Field Viewing camera. Following this, Rayleigh scattering calibration was carried out for the visible channels with these images after the appropriate data processing steps. To guarantee a high calibration precision, uncertainty was analyzed in advance taking into account ozone, aerosol optical depth (AOD), seawater salinity, chlorophyll concentration, wind speed and solar zenith angle. AOD and wind speed were found to be the biggest error sources, which were also closely coupled to the solar zenith angle. Therefore, the best sample data for Rayleigh scattering calibration were selected at the following solar zenith angle of 19–22° and wind speed of 5–13 m/s to reduce the reflection contributed by the water surface. The total Rayleigh scattering calibration uncertainties of visible bands are 2.44% (blue), 3.86% (green), and 4.63% (red) respectively. Compared with the recent field calibration results, the errors are −1.69% (blue), 1.83% (green), and −0.79% (red). Therefore, the Rayleigh scattering calibration can become an operational in-flight calibration method for the high spatial resolution satellites.