Two new calix[4]arene-based polymeric resins were synthesized via nucleophilic substitution reactions involving 5,11,17,23-tetrakis(N- piperidinomethyl)-25,26,27,28-tetrahydroxycalix[4]arene ( 2 ) and 5,11,17,23-tetrakis[4-carboethoxy-N-piperidino]-25,26,27,28-tetrahydroxycalix[4] arene ( 4 ) as precursors with Merrifield resin. Extraction studies were performed by liquid-liquid extraction and solid-liquid adsorption procedures. The monomeric compounds showed excellent extraction ability toward dichromate in liquid-liquid extraction systems. Polymeric resin 3 with calixarene moieties exhibited high adsorption properties, while resin 5 showed lower adsorption of dichromate in solid-liquid extractions.