An efficient chiral Bronsted acid-catalyzed enantioselective dehydrative Nazarov-type electrocyclization (DNE) of electron-rich aryl- and 2-thienyl-beta-amino-2-en-1-ols is described. The 4 pi conrotatory electrocyclization reaction affords access to a wide variety of the corresponding 1H-indenes and 4H-cyclopenta[b]thiophenes in excellent yields of up to 99% and enantiomeric excess (ee) values of up to 99%. Experimental and computational studies based on a proposed intimate contact ion pair species that is further assisted by hydrogen bonding between the amino group of the substrate cation and chiral catalyst anion provide insight into the observed product enantioselectivities.