The day/night band (DNB) of the Visible Infrared Imaging Radiometer Suite (VIIRS) onboard Suomi National Polar-orbiting Partnership (Suomi-NPP) represents a major advancement in night time imaging capabilities. DNB covers almost seven orders of magnitude in its dynamic range from full sunlight to half-moon. To achieve this large dynamic range, it uses four charge-coupled device arrays in three gain stages. The low gain stage (LGS) gain is calibrated using the solar diffuser. In operations, the medium and high gain stage values are determined by multiplying the gain ratios between the medium gain stage, and LGS, and high gain stage (HGS) and LGS, respectively. This paper focuses on independently verifying the radiometric accuracy and stability of DNB HGS using DNB observations of ground vicarious calibration sites under lunar illumination at night. Dome C in Antarctica in the southern hemisphere and Greenland in the northern hemisphere are chosen as the vicarious calibration sites. Nadir observations of these high latitude regions by VIIRS are selected during perpetual night season, i.e., from April to August for Dome C and from November to January for Greenland over the years 2012 to 2013. Additional selection criteria, such as lunar phase being more than half-moon and no influence of straylight effects, are also applied in data selection. The lunar spectral irradiance model, as a function of Sun–Earth–Moon distances and lunar phase, is used to determine the top-of-atmosphere reflectance at the vicarious site. The vicariously derived long-term reflectance from DNB observations agrees with the reflectance derived from Hyperion observations. The vicarious trending of DNB radiometric performance using DOME-C and Greenland under moon light shows that the DNB HGS radiometric variability (relative accuracy to lunar irradiance model and Hyperion observation) is within 8%. Residual variability is also discussed.