High chemical oxygen demand (COD) and a strong color, which primarily originates from desizing and dyeing operations, are two major removal objectives in textile wastewater treatment. In this study, crosslinking-induced precipitation via the covalent bonding between -OH groups of PVA and vinyl sulfone groups of reactive dyes is proposed to simultaneously remove poly(vinyl alcohol) (PVA) and reactive dyes. Due to the nucleophilic addition reaction under an alkaline condition, PVA polymers can be efficiently crosslinked by dye molecules and destabilized in the presence of alkali and Na2SO4. Additionally, due to the high coagulation efficiency under the alkaline conditions, MgSO4 was used as a coagulant to facilitate the removal of the residual color after precipitation. After a two-step process, whereby coagulation was followed by crosslinking-induced precipitation, the maximum efficiencies of the removal of COD, PVA, and color attained 88.9%, 86.3%, and 99.2%, respectively, when the PVA monomer/RB5 mole ratio was 400. We hope that this technically feasible, highly efficient, and cost-effective process provides a basis for the practical application of the simultaneous treatment of desizing and dyeing wastewater.