This article presents the synthesis and sorption characteristics of novel microspheres based on 4-vinylbenzene chloride (VBCl) with divinylbenzene (DVB) or ethylene glycol dimethylacrylate (EGDMA). To confirm the chemical structure of the homo- and co-polymers attenuated total reflectance, Fourier transform infrared spectroscopy (ATR-FTIR) was used. The presence of characteristic functional groups (−OH, −CH, −CH2, C−O, C=O and C–O–C) in obtained microspheres was confirmed. Differential scanning calorimetry (DSC) analysis confirms the good thermal resistance of the polymers. The decomposition of microspheres is closely related to the chemical structure of the monomers used. DVB-derived materials decompose in one step, whereas the decomposition of EGDMA derivatives is multi-stage. Obtained polymeric microspheres were applied for auramine O (AO) basic dye removal form aqueous solutions. Equilibrium studies confirmed that the Freundlich model described the system better than Langmuir or Temkin equations and the adsorption capacities kF ranged from 4.56 to 7.85 mg1−1/n L1/n/g. The sorption kinetic of AO from solutions of the 10 and 100 mg/L concentrations was very fast, and after 10 min, equilibrium was reached.