Spent coffee grounds and green coffee defective beans, which are industrial sub-products of coffee processing, have a potential use for cosmetic applications, due to their safety and high content in lipids that present interesting physicochemical properties. Sunscreen formulations in the form of water-in-oil emulsions might be a suitable application for these sub-products because providing a higher sun protection factor (SPF) for the same concentration of sunscreen activities than oil-in-water emulsions. The purpose of this work was to assess the biological effects of using the oil fraction of spent coffee grounds extracted with supercritical CO2 and green coffee oil in the development of new generation of sunscreens with improved sun protection performance. The oil fractions were used to prepare w/o sunscreens involving a cold emulsification process, with purified water as disperse aqueous phase and TiO2 and ZnO particles as stabilizers. The sunscreens were characterized in terms of mechanical, rheological and skin adhesion properties. In addition, the in vitro and in vivo biological properties of the formulations were evaluated, including safety and sunscreen water resistance tests. The use of two types of solid particles proved to be useful in the developed formulations, ensuring a high SPF with UVB/A protection, conferred by TiO2 and ZnO, respectively. Moreover, the emulsion containing 35% w/w of the spent coffee grounds oil fraction presented promising characteristics in the improvement of water performance with a broad spectrum sun protection when compared to an emulsion containing 35% w/w of green coffee oil which improved the SPF in physical sunscreens. The formulations are industrial-scalable and suitable for topical use according to the rheological, mechanical and safety assessment. The use of spent coffee oil in cosmetic industry seems to be a suitable approach for the valorisation of waste from the coffee industry and presents promising characteristics in the improvement of sunscreen performance.