The aim of this paper is to analyze the suitability of the high-mountain stations Mauna Loa and Izaña for Langley plot calibration of Sun photometers. Thus the aerosol optical depth (AOD) characteristics and seasonality, as well as the cloudiness, have been investigated in order to provide a robust estimation of the calibration uncertainty as well as the number of days that are suitable for Langley calibrations. The data used for the investigations belong to the AERONET and GAW-PFR networks, which maintain reference Sun photometers at these stations with long measurement records: 22 years at Mauna Loa and 15 years at Izaña. In terms of clear-sky and stable aerosol conditions, Mauna Loa (3397 m a.s.l.) exhibits on average 377 Langley plots (243 morning and 134 afternoon) per year suitable for Langley plot calibration, whereas Izaña (2373 m a.s.l.) shows 343 Langley plots (187 morning and 155 afternoon) per year. The background AOD (500 nm) values, on days that are favorable for Langley calibrations, are in the range 0.01–0.02 throughout the year, with well-defined seasonality that exhibits a spring maximum at both stations plus a slight summer increase at Izaña. The statistical analysis of the long-term determination of extraterrestrial signals yields to a calibration uncertainty of ∼ 0.25–0.5 %, this uncertainty being smaller in the visible and near-infrared wavelengths and larger in the ultraviolet wavelengths. This is due to atmospheric variability produced by changes in several factors, mainly the AOD. The uncertainty cannot be reduced based only on quality criteria of individual Langley plots and averaging over several days is shown to reduce the uncertainty to the needed levels for reference Sun photometers.