Random copolymers of poly(ethylene glycol) methacrylate (PEGM), and diethyl amino ethyl methacrylate (DEAEM) were synthesized at low, and high conversions by photoinitiation. Crosslinked poly(PEGM‐co‐DEAEM) samples were obtained, and characterized by FTIR, SEM, DSC, TGA, and elemental analyses. Swelling behavior of the copolymers revealed that the copolymers acted as superabsorbent hydrogels. The monomer reactivity ratios were calculated using Fineman Ross, Extended Kelen Tüdøs, and Mayo Lewis methods that gave r1(PEGM) = 0.90, r2(DEAEM) = 0.14 at low conversions. At high conversions r1 and r2 values were calculated as 1.01 and 0.40, respectively. Adsorption isotherms of methyl orange (MO) onto hydrogels were studied using Langmuir, Freundlich, and Temkin models. The experimental data fitted well with the Langmuir equation. The maximum adsorption capacity for MO was 212.7 mg g−1 at pH = 3. The adsorption data gave best fit with the pseudo‐second order kinetic model. Thermodynamic evaluation showed spontaneous nature for MO adsorption onto poly(PEGM‐co‐DEAEM) hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47707.