This study compared the effectiveness of different biosorbents, viz. materials commonly present in natural treatment systems (Scenedesmus quadricauda and reed) and commonly produced fruit wastes (orange and banana peel) to remove Cr(III) and Cr(VI) from a synthetic wastewater simulating tannery wastewater. The Cr(III) removal efficiency followed the order S. quadricauda > orange peel > banana peel > reed, whereas the Cr(VI) removal followed the order banana peel > S. quadricauda > reed > orange peel. The chromium biosorption kinetics were governed by the intraparticle diffusion mechanism. Isotherm data obtained using the different biosorbents were fitted to the Langmuir, Freundlich, and SIPS models, revealing that the experimental data followed most closely the monolayer sorption theory-based Langmuir model than the other models. The maximum Cr(III) sorption capacity, calculated using the Langmuir model, was found to be 12 and 9 mg/g for S. quadricauda and orange peel, respectively, and the maximum Cr(VI) sorption capacity calculated for banana peel was 3 mg/g. The influence of biosorbent size, pH, solid–liquid ratio, and competing ions were examined for Cr(III) biosorption by S. quadricauda and orange peel and for Cr(VI) sorption by banana peel. The solution pH was found to be the most influential parameter affecting the biosorption process: whereas pH 5 was found to be optimum for maximum removal of Cr(III), Cr(VI) was best removed at a pH as low as 3. Interference to chromium sorption by various ions revealed that Cr(III) binding onto orange peel occurs through electrostatic forces, whereas Cr(VI) binding onto banana peel through non-electrostatic forces.