The visible-shortwave infrared Advanced Hyperspectral Imager (AHSI) is a payload onboard the Gaofen-5 satellite, which is China’s first hyperspectral satellite and is part of the Chinese High-Resolution Earth Observation System. As a supplement to the onboard radiometric calibration of the AHSI instrument, vicarious calibration is also required, which is independent of the instrument-based calibration. In this article, a reflectance-based vicarious calibration approach is presented, which takes surface reflectance data, aerosol data, and atmospheric water vapor data into account. The Dunhuang test site, which is one of the China Radiometric Calibration Sites (CRCS) for the vicarious calibration of spaceborne sensors, possesses stable, uniform, and measurable surface objects, so it was chosen as the radiation source to replace the laboratory and onboard calibrators. A Spectra Vista Corporation (SVC) spectral radiometer and a CE318 sun photometer were utilized for the measurement of the surface reflectance and the condition of the aerosol, respectively. The radiance at the entrance pupil at the top of atmosphere was then obtained through the MODerate resolution atmospheric TRANsmission (MODTRAN) atmospheric transmission model. The surface reflectance was obtained using the Fast Line-of-sight Atmospheric Analysis of Hypercubes (FLAASH) atmospheric model for validation. The results show that, with regard to the calibration coefficients, the calibrated AHSI instrument presents a stable radiometric performance among different land-cover types. The ratios on all the bands are between 0.8 and 1.2 and are consistent with the reflectance data from the Dunhuang test site. The <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${R} ^{{2}}$ </tex-math></inline-formula> values are all greater than 0.95 and the spectral angle is all less than 2°. The standard deviations of the ratios are less than 3% for each chosen band, which proves that the calibrated data have a high consistency with the <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">in situ</i> measurements. When compared with Landsat 8 and Sentinel-2, the mean errors of the surface reflectance are all under 0.06, which further demonstrates that the calibrated reflectance has a high accuracy.