Understanding the uncertainty of a vicarious calibration is essential for any application to Earth imaging sensors. The Radiometric Calibration Network provides SI-traceable spectral top-of-atmosphere (TOA) reflectance from a network of ground sites and uses a look-up table (LUT) approach for uncertainty determination. The uncertainty LUT was derived using Monte Carlo techniques applied to the relevant solar geometry, surface, and atmospheric variables. While surface reflectance is typically the dominant uncertainty source, atmospheric contributions do play an important role, depending upon the exact scenario and conditions. This approach allows knowledge of TOA reflectance uncertainty to within 0.5%.