Our study aimed to characterize the composition of the ethyl acetate extract obtained from Centaurea acaulis L. and assess its dermatoprotective and antioxidant properties. The secondary metabolite composition was established by high-performance liquid chromatography combined with mass spectrometry. The antioxidant activity was assessed using four different assays, including DPPH, β-carotene, CUPRAC, and reducing power assays. Furthermore, the in vitro photoprotective effect was evaluated by measuring sun protection. The HPLC-TOF/MS analysis identified the presence of 19 bioactive compounds in the ethyl acetate extract. Major components such as rosmarinic acid and 4-hydroxy benzoic acid were detected, along with other compounds including caffeic acid, cichoric acid, gentisic acid, p-coumaric acid, protocatechuic acid, ferulic acid, vanilic acid, gallic acid, apigenin-7-glucoside, catechin, kaempferol, and quercetin. The ethyl acetate extract of Centaurea acaulis L. exhibited strong antioxidant activity in DPPH, β-carotene, CUPRAC, and reducing power assays, outperforming standard antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA), tannic acid, and ascorbic acid. Additionally, the extract demonstrated a high ability to absorb UV radiation, with an average sun protection factor of 40.20 ± 0.11. These findings highlight the significant antioxidant and dermatoprotective potential of the ethyl acetate extract from Centaurea acaulis L., suggesting its potential use in cosmetic and dietary additive formulations.