Grape pomace retains polyphenols in the peels and in the seeds after winemaking, which is indicative of the high valorization potential of this industrial waste. There is strong evidence that phenolics are robust antioxidants and confer photoprotection; thus, it is rational to apply these active compounds from winemaking waste to sunscreens, in order to increase UV protection. Despite the importance of this class of cosmetics to public health, more efficacious strategies are still needed to overcome the problems caused by the photoinstability of some UV filters. The hydroethanolic extract of Vitis vinifera L. grapes was obtained by percolation and then lyophilized. Six formulations were developed: Type I—cosmetic base and UV filters; Type II—cosmetic base and extract; and Type III—cosmetic base, extract and UV filters. Each formulation was prepared in the pHs 5 and 7. The antioxidant activities of the samples were measured by DPPH• and expressed in Trolox® equivalents (TE), and their photostability and in vitro sun protection factor (SPF) were analyzed by diffuse reflectance spectrophotometry. The anti-radical efficiencies observed in the formulations with grape extract were: (II) 590.12 ± 0.01 μmol TE g’1 at pH 5 and 424.51 ± 0.32 μmol TE g’1 at pH 7; (III) 550.88 ± 0.00 μmol TE g’1 at pH 5 and 429.66 ± 0.10 μmol TE g’1, at pH 7, demonstrating that the UV filters, butylmethoxydibenzoyl methane, ethylhexyl methoxycinnamate and ethylhexyl dimethyl 4-aminobenzoic acid had no influence on this effect. The photoprotective efficacy and the photostability of formulation III containing the extract and UV filters at pH 5 suggested that a synergism between the active molecules provided an 81% increase in SPF. Additionally, this was the only sample that maintained a broad spectrum of protection after irradiation. These results confirmed that the grape pomace extract has multifunctional potential for cosmetic use, mainly in sunscreens, granting them superior performance. View Full-Text.