With the rapid advancement of three dimensional (3D) printing technology that offers flexibility to achieve desired surface area and permeability for wastewater applications, structural topology design has the potential to significantly improve the adsorption performance. This present work involves fabricating the green water technology with four different complex monolithic structural designs (Kagome, gyroid, Fischer, and body‐centered cubic [BCC]) with specific surface areas varied from 19.4 to 39.84 mm2 via digital light processing (DLP) technique. All the monolithic structures with different structural topologies were grafted with chitosan to evaluate their adsorption performance in a batch process. The influence of different structural topology on the adsorption performance and efficiency was evaluated at an optimal temperature of 60°C with optimum pH of 6.3 for a reaction time of 2 h using synthetic methyl orange (MO) dye and textile wastewater. Results indicated that the body‐centered cubic (BCC) design exhibited the highest MO adsorption capacity (12.71 mg/g), with the highest permeability (2.5710−7 m2) and surface area (39.84 mm2). Additionally, a direct relationship was found between the surface area and the permeability of the adsorbent as well as adsorption strength. Fifty percent of color and 2.46% of chemical oxygen demand (COD) removal efficiencies were achieved to verify the adsorbent feasibility in actual application. The present work mainly establishes the feasibility of 3D printing in fabricating different monolithic structures, which enables future topology optimization for improved wastewater management.