Dermal synthesis, following sun exposure, is the main source of vitamin D. This study characterizes ambient UVB radiation relevant for vitamin D production in Europe. A biological weighing function was applied to data from the Tropospheric Emissions Monitoring Internet Service (TEMIS) for 46 capital cities over an 18-year period (2004–2021) to isolate wavelengths relevant for vitamin D production (D-UVB). Cumulative and weighted D-UVB (CW-D-UVB) were calculated to approximate seasonal vitamin D accumulation and diminution. Monthly 25(OH)D concentration measurements were extracted from published reports. All data were analyzed by location and time. Despite a moderate latitudinal range (35–64° N), we observed large—up to five-fold—regional differences: the highest mean diurnal D-UVB dose of 5.57 kJ/m2 (SD = 3.55 kJ/m2) was observed in Nicosia (Cyprus) and the lowest in Reykjavik (Iceland, 1.16 ± 1.29 kJ/m2). Seasonal differences in diurnal D-UVB dose were even more pronounced, with a median 36-fold difference between annual peak and trough depending on a location (range: 10- to 525-fold). The mean duration of “vitamin D winter” was 126 days but varied widely (4 to 215 days). Monthly CW-D-UVB and 25(OH)D changes were very strongly correlated: the changes in 25(OH)D concentration increased by 12.6 nmol/L for every 100 kJ/m2 increment of CW-D-UVB in population-based studies (r2 = 0.79, p-value = 1.16 × 10−37). Understanding the differences in D-UVB radiation can help understand determinants of vitamin D status and guide region- and season-specific safe and effective sunlight exposure recommendations and vitamin D supplementation guidelines.