Pillar[n]arenesareanewkindofsupramolecularmacrocyclichostswhichhavedevelopedrapidlyduetotheiruniquetopologyandhighfunctionality,givingrisetomanyapplicationsintheconstructionofinterestingandfunctionalmaterials.Amongthem,water-solublepillar[n]arenesbearingtriethyleneoxide(TEO)chainshavedrawnincreasingresearchinterestduetotheiradvantageousproperties.Inthisreview,wesummarizedtherecentprogressofdynamicmaterialsfabricatedfromwatersolublepillar[n]arenesbearingTEOgroups,includingthermoresponsivematerialswithlowercriticalsolutiontemperature(LCST)behavior,cyclichostliquids,andsmartwindows.Itisanticipatedthatmoreandmore‘smart’supramolecularmaterialsbasedonmodifiedpillar[n]areneswillbedevelopedinthisburgeoningareaofresearch.