A novel hydrophilic porous alginate-based polyHIPE (AGA) was synthesized via an oil-in-water emulsion templating approach. AGA was used as an adsorbent for removing methylene blue (MB) dye in single- and multi-dye systems. BET, SEM, FTIR, XRD, and TEM were used to characterize AGA to elucidate its morphology, composition and physicochemical properties. According to the results, 1.25 g/L AGA adsorbed 99 % of 10 mg/L MB in 3 h in a single-dye system. The removal efficiency decreased to 97.2 % in the presence of 10 mg/L Cu2+ ions and 40.2 % when the solution salinity increased to 70 %. In a single-dye system, the experimental data do not match well with the Freundlich isotherm, pseudo-first order, and the Elovich kinetic model, however, in a multi-dye system, it fit well with both extended Langmuir and the Sheindorf-Rebhun-Sheintuch. Notably, AGA removed 66.87 mg/g in a dye solution containing only MB, whereas 50.14–60.01 mg/g adsorption of MB was accomplished in a multiple-dye system. According to the molecular docking analysis, the dye removal process involved chemical bonds between the functional groups of AGA and the dye molecules, hydrogen bonds, hydrophobic and electrostatic interactions. The overall binding score of MB decreased from −26.9 kcal/mol in a single-dye system to −18.3 kcal/mol in a ternary system.