In the present study we assessed the effects of ambient solar UV exclusion on leaf physiology, and leaf and berry skin phenolic composition, of a major grapevine cultivar (Tempranillo) grown under typically Mediterranean field conditions over an entire season. In general, the effects of time were stronger than those of UV radiation. Ambient UV caused a little stressing effect (eustress) on leaf physiology, with decreasing net photosynthesis rates and stomatal conductances. However, it was not accompanied by alterations in Fv/Fm or photosynthetic pigments, and was partially counterbalanced by the UV-induced accumulation of protective flavonols. Consequently, Tempranillo leaves are notably adapted to current UV levels. The responses of berry skin phenolic compounds were diverse, moderate, and mostly transitory. At harvest, the clearest response in UV-exposed berries was again flavonol accumulation, together with a decrease in the flavonol hydroxylation level. Contrarily, responses of anthocyanins, flavanols, stilbenes and hydroxycinnamic derivatives were much more subtle or nonexistent. Kaempferols were the only compounds whose leaf and berry skin contents were correlated, which suggests a mostly different regulation of phenolic metabolism for each organ. Interestingly, the dose of biologically effective UV radiation (UVBE) was correlated with the leaf and berry skin contents of quercetins and kaempferols; relationships were linear except for the exponential relationship between UVBE dose and berry skin kaempferols. This opens management possibilities to modify kaempferol and quercetin contents in grapevine through UV manipulation.