Due to the existence of new methodologies that have reduced the production costs of microbiological chitosan, this paper puts forward the use of agro-industrial residues in order to produce microbiological chitosan and to apply chitosan as an innovative resource for removing acid orange 7 (AO7) from wastewaters. The best culture conditions were selected by a full 24 factorial design, and the removal of the dye was optimized by a 23 central composite rotational design. The results showed that corn steep liquor (CSL) is an agro-industrial residue that can be advantageously used to produce microbiological chitosan with yields up to 7.8 g/kg of substrate. FT-IR spectra of the product showed typical peak distributions like those of standard chitosan which confirmed the extracted product was chitosan-like. The efficiency of removing low concentrations of AO7 by using microbiological chitosan in distilled water (up to 89.96%) and tap water (up to 80.60%) was significantly higher than the efficiency of the control (chitosan obtained from crustaceans), suggesting that this biopolymer is a better economic alternative for discoloring wastewater where a low concentration of the dye is considered toxic. The high percentage recovery of AO7 from the microbiological chitosan particles used favors this biopolymer as a possible bleaching agent which may be reusable.