The residues generated after the extraction of agar from Gelidium sesquipedale by means of a hot-water treatment, with (NaOH+HW residue) and without (HW residue) an alkali pre-treatment have been valorized to produce high performance cellulosic films. Both residues were mainly composed of structural carbohydrates (in particular, agar), ashes and lipids. The residual agar could only be completely removed by applying a two-step process based on bleaching and alkaline treatments. The application of the alkaline pre-treatment for the extraction of agar did not significantly affect the properties of the films produced from the extracted fractions, hence making the HW residue more sustainable and economically viable. The agar remaining in the less purified fractions had a positive effect on the performance of the films, improving their transparency, mechanical properties and water vapour barrier, out-performing benchmark biopolymers; in addition, these materials presented antioxidant capacity inhibiting the degradation of ß-carotene.