Chemical modification of sisal fibers via in situ oxidative polymerization of aniline was conducted to examine their defluoridation capacity for fluoride from drinking water. The effects of polyaniline modifications have shown significant changes on the chemical moieties and defluoridation capacity of sisal fibers (SFs). FTIR peaks at 1440 cm⁻¹ and 1560 cm⁻¹ revealed the presence of benzoid and quinoid structures together with sisal fiber (SF). Thermal profiles confirmed the enhancement of thermal stability of polyaniline‐modified sisal fibers (PAniMSFs). SEM microstructure also proved the surface roughening of SFs as a result of polyaniline modifications. Optimal batch adsorption parameters (pH, contact time, adsorbent dose, and initial concentration) were found to be 5, 60 min, 1 g, and 10 mg/L, respectively. Adsorption kinetics proved that the removal of fluoride follows pseudo‐second‐order model (K₂ = 0.18 g. (mg·min)⁻¹), while the adsorption isotherm well described by the Langmuir and Freundlich model with an experimental adsorption capacity of 2.49 mg/g. Hence, modifications and improvements are required to reduce the amount of fluoride to a permissible level and enhance the longevity and activity of adsorbent materials.