A polystyrene with pendant calixpyrroles was prepared via ‘click reaction’ strategy. First, a poly(styrene-co-chloromethylstyrene) with approximately 12% of chloro groups was prepared by conventional free radical polymerisation. The chloro groups were then converted to azido groups using NaN3 in N,N-dimethylformamide. An alkyne-functionalised calixpyrrole was then coupled to the azido-functionalised polystyrene by click chemistry with high efficiency. The resulting polystyrene with pendant calixpyrroles was used to extract fluoride and chloride anions (as their tetrabutylammonium salts) from their aqueous solutions to organic media.