This study describes the tethering of dimethylamionomethyl bonded calixarene (DMAM-calixarene) onto cotton fabric surface functionalized with poly(glycidyl methacrylate) (PGMA) linker layer using initiated chemical vapor deposition (iCVD) technique and the efficient adsorption capability of DMAM-calixarene functional textiles for the toxic hexavalent chromium from polluted water. The characterization of DMAM-calixarene-tethered textile fabric was performed by FTIR and XPS spectroscopy. Cr(VI) solutions was passed over packed DMAM-calixarene-tethered textile fabric adsorbent and the highest adsorption was observed at pH 2 in dichromate anion form of COS. The regeneration and selectivity studies indicate that the DMAM-calixarene-tethered textile fabric has outstanding adsorbent features in used experimental conditions for hexavalent chromium. Moreover, it was observed that both H-bonding and electrostatic interactions were significant factors in the dichromate anion adsorption process. Thus, this study clearly revealed that any DMAM-calixarene-tethered textile fabric can be easily used as a selective hexavalent chromium capture filter in geographic regions lacking appropriate wastewater purification systems.