In our study’s scenario, flexible films were fabricated from TEMPO-oxidized cellulose nanofibers and silver selenide (CNF/Ag2Se) as efficient membranes for the degradation of methylene blue (MB). Different concentrations of Ag2Se particles were in situ prepared in the presence of CNF. The in-situ synthesis of Ag2Se nanoparticles in the presence of CNF was reported as efficient technique for the formation of submicrosize Ag2Se particles with a narrow size distribution and homogeneous dispersion onto CNF. TEM analysis revealed that the nanofibers had uniform width and diameter, while XRD demonstrated single-phase orthorhombic β-Ag2Se formation. 3D-FESEM showed tiny root measurer values of 28, 30, and 32.56 nm in polymeric films with 2.5, 5, and 10% Ag2Se-filled CNF. Polymeric films had visible-driven-light photocatalytic activity because the band gap fell from 4.61 eV (UV area) to 2.71 eV (visible region). The composite’s photocatalytic performance was assessed by MB degradation. 10% of CNF/Ag2Se demonstrated maximal photocatalytic activity under simulated sunlight for 60 min, pH 9, and 3 g/L composite weight. The factorial design statistical analysis showed that MB dye photodegradation is mostly affected by irradiation time and dye concentration. Environmental, social, and economic factors are all considered, making this study suitable for implementing photocatalysis to large-scale water treatment systems, which is a key component of sustainability.