An efficient synthesis of pillar [5] - and pillar [6] arenes with alkyl substituents of various lengths from commercially available reagents (1,4-dialkoxybenzene and paraformaldehyde or 1,3,5-trioxane in the presence of Lewis acids) has been worked out. Cyclooligomerization products were isolated in high yields and with high oligoselectivity. In the presence of acetylcholine 1,4-bis(dodecyloxy)pillar[5]arene forms the inclusion complex in the ratio 1:1, which is observed by 1Н NMR method.