This study describes the synthesis of calix[6]arene (C6) appended Amberlite XAD-4 resin and its application for the removal of anthraquinone-based reactive blue 19 (RB-19) dye from aqueous environments. The C6-resin 5 was characterized with various analytical techniques, including Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and elemental analysis. Adsorption experiments were carried out to investigate the effects of the pH, adsorbent dosage, electrolyte, contact time, and temperature on the adsorption of RB-19 dye onto the C6-resin 5. From the results, we observed that the percentage adsorption of the RB-19 dye was highly dependent on the concentration of electrolyte and the pH of the solution. The maximum adsorption was achieved at pH 9. The thermal study demonstrated that the adsorption process was endothermic and spontaneous in nature. The isothermic study showed that the adsorption behavior could be better demonstrated by the Langmuir and Dubinin and Radushkevich isotherm model. From field studies, it has been concluded that C6-resin 5 is an effective adsorbent for the removal of RB-19 dye.