Although recent work has shown natural lignin products are promising to fabricate various polymer based functional composites, high-value applications were challenged by their structural complexity and inhomogeneity. This work specially assessed the potential of four technical lignins for cellulose based functional films production. These four technical lignins were obtained by emerging pretreatment systems, i.e., lactic acid-betaine deep eutectic solvent (DES), ethanol organosolv, soda/anthraquinone (Soda/AQ) and the sodium salicylate hydrotrope, and their phenolic substructures were comparatively identified by prevalent ³¹P NMR technique. The influence of lignin chemical structure on the antioxidant potential and UV-shielding performance of the prepared cellulose/technical lignin composite films were assessed. Results showed severe organosolv and soda/AQ pretreatment produced technical lignins with higher total phenolic hydroxyl groups (3.37 and 3.23 mmol g-1 respectively), which also exhibited higher antioxidant activities. The composite films could effectively block the ultraviolet lights especially for UVB region (ultraviolet B, 280–315 nm) at only 5 wt.% lignin content. The contribution of lignin phenolic substructures to both antioxidant activity and UV-shielding property from high to low was syringyl > guaiacyl > p-hydroxyphenyl phenolic hydroxyl groups. This work provided some useful information that could facilitate upstream lignin extraction or downstream value-added applications.