A formulated photocurable poly(ethylene glycol) diacrylate (PEGDA) and 2‐hydroxylethyl methacrylate (HEMA) polymer matrix (PEGDA:HEMA) was developed for constructing an adsorptive 3D cubic monolith using masked stereolithography (MSLA) 3D‐printing technique. A pure PEGDA formulation served as a control in comparative studies. Additionally, two structural designs (solid cube and cubic lattice) were also quantitatively compared to determine the adsorption performance for Rhodamine B (RhB) dye removal. Results indicated that the cubic lattice formulated with hydrophilic PEGDA:HEMA (θ~47.20°) was more effective at removing RhB dye. Additionally, the preliminary study identified pH 9 as the optimal level for RhB dye removal using 3D cubic monolith for both formulations. A Taguchi orthogonal array of L9 (33) was used to concurrently vary three parameters: adsorbent dosage (0.65 ± 0.02 g per cubic lattice), operating temperature (30°C, 40°C, and 50°C), and initial RhB concentration (20, 60, and 100 ppm). The highest mean of the signal‐to‐noise (S/N) ratio was chosen to obtain the highest adsorption performance. The removal efficiency (R%) of RhB dye ranged from 44.48% to 94.86%, and the adsorption capacity (K) ranged from 0.59 to 3.73 (mg/g) after 5 h. Seven adsorption isotherms and five adsorption kinetics modelling were performed. Adsorption isotherm data fitted well with the Redlich–Peterson model for both linear (R2 = 0.998) and nonlinear (R2 = 1). Besides that, the pseudo‐second‐order model (PSO) accurately described adsorption kinetics (R2 = 0.995). The separation factor (RL) confirmed favourable adsorption (0 < RL < 1). Thermodynamic parameters indicated that the adsorption process was endothermic and at higher temperatures, entropy increased. Also, the 3D–printed PEGDA:HEMA cubic lattice exhibited good mechanical stability. Furthermore, the 3D PEGA: HEMA lattice has the ability to be used in several adsorption cycles of degrading RhB dye. Ultimately, the present work demonstrates the viability of 3D printing photocurable PEGDA:HEMA resin and utilizes statistical tools to optimize process parameters, enhancing predictability for wastewater management.