A new phosphorus-containing sorbent was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) and trimethylvinyl silane (TMVS) with diphenylvinylphoshine oxide (DPVO). It was characterized and applied in the removal of cationic dyes such as C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) and C.I. Basic Red 46 (BR46) using the batch method. Spectroscopic analysis indicated that the phosphinoyl group was introduced into the sorbent structure. Equilibrium adsorption data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The Freundlich model is the most suitable to describe the adsorption of BB3 (the Freundlich constant kF = 32.3 mg1−1/nL1/n/g) and BY2 on the sorbent (13.8 mg1−1/nL1/n/g), while the Langmuir model is the most adequate to describe the adsorption of BR46 (the monolayer capacity Q0 = 2.7 mg/g). The kinetics of the dye adsorption follows the assumptions of the pseudo-second-order (the rate constants k2 = 0.087 ÷ 0.738 g/mg min) model rather than pseudo-first-order or intraparticle diffusion. The presence of Na2SO4 and cationic surfactant in the aqueous solutions inhibited dye retention by the DPVO–EGDMA–TMVS. Adsorbent regeneration efficiency does not exceed 60% using 1 M NaCl and 1 M HCl solutions in the presence of 50% v/v methanol.