The ultraviolet radiation index (UV index–UVI) is a dimensionless indicator that informs the intensity of ultraviolet radiation on the Earth’s surface. It makes it easier for people to assess UV levels and understand how to protect themselves from excessive Sun exposure. In Brazil, however, the information regarding UV is scarce, with low spatial and temporal coverage. Thus, continuous monitoring is conducted through satellites, although ground-based monitoring of UV is more accurate than satellite retrievals, and comparisons are necessary for validation. This paper aims to compare the levels of UV index measured on the ground and by satellite (OMI and GOME-2) over Natal, Brazil (05.78°S; 35.21°W) from 2005 to 2022. The comparison was made under clear-sky conditions using METAR cloud cover and LER data. Characterization of the diurnal and seasonal variability of the ground-based UV index levels under all and clear-sky conditions is also reported. The analysis indicates that in Natal, noontime all-sky UV index levels were 6.8% higher during periods of prevalent broken clouds. The two satellite sources (OMI noontime and overpass) and GOME-2 noontime are reliable sources for UV index, which show good agreement with ground-based measurements, with UVI estimated from OMI both at the overpass and noontime being less biased than GOME-2-estimated UVI. Such a process of data verification is important should these data be used for long-term trend analysis or the monitoring of UV exposure risk and possible impacts on human health.