A hybrid monolithic column with sulfonate functionality was successfully prepared for the simultaneous separation of common inorganic cations in ion-exchange chromatographic mode through a simple and easy single-step preparation method. The strong cation-exchange moieties were provided directly from allylsulfonate, which worked as an organic monomer in the single-step reaction. Inorganic cations (Li(+), Na(+), K(+), NH4(+), Cs(+), Rb(+), Mg(2+), Ca(2+), and Sr(2+)) were separated satisfactorily by using CuSO4 as the eluent with indirect UV detection. The allysulfonate hybrid monolith showed a better performance in terms of speed and pressure drop than the capillary packed column. The number of theoretical plates achieved was 19,017 plates/m (in the case of NH4(+) as the analyte). The relative standard deviations (n = 6) of both retention time and peak height were less than 1.96% for all the analyte cations. The allysulfonate hybrid monolithic column was successfully applied for the rapid and simultaneous separation of inorganic cations in groundwater and the effluent of onsite domestic wastewater treatment system.