The aim of this study was to assess solar ultraviolet radiation (UVR) doses received by the eyes in different exposure situations, and to predict the sun protection effectiveness provided by various styles of sunglasses at facial, periorbital, and ocular skin zones including the cornea and accounting for different head positions. A 3D numeric model was optimized to predict direct, diffuse and reflected erythemally weighted UVR doses received at various skin zones. Precisely defined facial, periorbital, and ocular skin zones, sunglasses (goggles, medium-, and large-sized sunglasses) and three head positions were modeled to simulate daily (08:00–17:00) and midday (12:00–14:00) UVR doses. The shading from sunglasses’ frame and lenses’ UVR transmission were used to calculate a predictive protection factor (PPF [%]). Highest ocular daily UVR doses were estimated at the uncovered cornea (1718.4 J/m2). Least sun protection was provided by middle-sized sunglasses with highest midday dose at the white lateral (290.8 J/m2) and lateral periorbital zones (390.9 J/m2). Goggles reached almost 100% protection at all skin zones. Large-sized sunglasses were highly effective in winter; however, their effectiveness depended on diffuse UVR doses received. In “looking-up” head positions highest midday UVR doses were received at the unprotected cornea (908.1 J/m2), totally protected when large-sized sunglasses are used. All tested sunglass lenses fully blocked UVR. Sunglasses’ protection effectiveness is strongly influenced by geometry, wearing position, head positions, and exposure conditions. Sunglasses do not totally block UVR and should be combined with additional protection means. 3D modeling allows estimating UVR exposure of highly sensitive small skin zones, chronically exposed and rarely assessed.