The aim of this work is the study of the sky conditions climatology over Greece based on the diffuse-fraction (kd) limits, for clear, kd ∈ [0, 0.26]; intermediate, kd ∈ (0.26, 0.78); and overcast, kd ∈ (0.78, 1) skies. kd is, therefore, used here to characterise the sky conditions over a site. Its values are estimated from diffuse and global horizontal solar irradiances the typical meteorological years of 43 selected Greek sites. The kd values in each specific range are equivalent to sunshine durations (SSDs) under the particular sky conditions. Annual, seasonal, and intra-annual variations in SSDs are estimated with regression equations to fit their means. Clear skies comprise 33%, intermediate 40%, and overcast 27% of the time in a year. kd, as an atmospheric scattering index (ASI), shows dependence on the sites’ geographical latitude: best-fit lines mean ASIs are derived showing no trend, while overcast skies show a slight negative trend. A comparison of the clear-sky SSDs for four Greek sites from the Global Climate Data and one site from the Academy of Sciences of Moldova with those derived from kd shows a remarkable difference. A new methodology is developed that results in much smaller differences. Finally, maps of the annual SSDs and ASIs are derived for Greece.