The on-orbit radiometric calibration of the reflective solar bands (RSBs) of the Visible Infrared Imaging Radiometer Suite (VIIRS) aboard the Suomi National Polar-orbiting Partnership satellite is carried out primarily through observations of a fully illuminated solar diffuser (SD) panel. Accurate knowledge of the solar spectral radiance scattered from the SD is available. The sensor aperture spectral radiance is assumed to be a quadratic polynomial function of a VIIRS detector's background-subtracted response in digital number. The coefficients of the polynomial were initially determined prelaunch. Once on orbit, we assume that these coefficients change uniformly by a common calibration factor, which is referred to as the F-factor. The known solar spectral radiance scattered from a fully illuminated SD allows for the determination of these F-factors. We describe the methodology and the associated algorithms used in the calculation of the RSB F-factors. Our results show that the F-factors change over time, with the largest change occurring at a wavelength of 862 nm (with a value of about 1.55 on day 950 after the satellite launch, relative to its value at the beginning of the launch). In addition, we estimate the relative error standard deviations of the computed top-of-the-atmosphere reflectance at the detector pixel level. On day 950 of the mission, the relative error standard deviations are all less or equal to 0.016, except for the M11 band (band central wavelength of 2257 nm) , which has a relative error standard deviation of about 0.049 due to a very low signal-to-noise ratio.