This study involves a synthesis of bentonite/polyaniline composite (BE/PANI) of enhanced physicochemical properties as catalyst support for Ni2O3 photocatalyst. The change in the structural properties, morphological features, and optical behavior was addressed utilizing several analytic techniques. The characterization results reflected considerable enhancement in the specific surface area after the integration between bentonite and polyaniline (127m2/g) and after loading of the campsite by Ni2O3 forming bentonite/polyaniline@Ni2O3 composite (BE/PANI@Ni2O3) (231m2/g). Additionally, the band gap energy was reduced to 2.41eV and 1.61eV for BE/PANI and BE/PANI@Ni2O3, respectively, as compared to that of 3.4eV for pure Ni2O3. The photocatalytic removal of safranin-O dye under sunlight exposure using BE/PANI@Ni2O3 as catalyst revealed great enhancement in the removal percentages by 63%, 75%, and 72.35% higher than bentonite, polyaniline, and Ni2O3, respectively. Five milligrams per liter of safranin-O dye can be completely removed from 100ml water using 0.05g of the composite after 90min. The catalyst also was applied effectively in the removal of safranin-O dye from raw water samples as a realistic application of the synthetic composite. Synthetic BE/PANI@Ni2O3 as photocatalyst showed very high stability and can be used seven times as photocatalytic at amazing removal percentages.