Calixpyrrole-based oligomeric compounds were synthesized by “click chemistry” from the corresponding alkyne- and azide-functionalized calixpyrroles. Calixpyrrole 3, possessing an alkyne functional group, was prepared through a mixed condensation of pyrrole with acetone and but-3-ynyl 4-oxopentanoate. Another alkyne-group-containing calixpyrrole 5 was obtained by treatment of 4′-hydroxyphenyl-functionalized calixpyrrole 4 with propargyl bromide. Tetrakis(azidopentyl)-functionalized calixpyrrole 7 was synthesized by reacting NaN3 with tetrabromopentyltetraethylcalixpyrrole 6, which was prepared through a condensation reaction of pyrrole and 7-bromohept-2-one. Oligomeric calixpyrrole compounds were found to be capable of extracting tetrabutylammonium chloride and fluoride salts from aqueous media. Extraction abilities of the oligomeric compounds were monitored by NMR and UV/Vis spectroscopy and thermogravimetric analysis.