Hourly measurements of solar irradiance in the wave band excluding photosynthetically active radiation (PAR) and solar irradiance (SI) were made over a 12-month period at the National Observatory of Athens, for obtaining the ratios of PAR to SI. These irradiance ratios exhibit dependence on sky conditions, with slightly larger values being observed under “cloudy” skies and seasonal variations, attributable to changes in local air mass climatology. The highest values have been obtained during the growing season (April–September). The mean annual value of 0.473 observed for the irradiance ratio in the PAR band compares favorably with values reported in the literature for different locations over a wide geographical area.