Various pillar[5]arenes of different substituents with varying electronic properties were synthesized. The synthetic strategy involved two main steps; synthesis of 1,4 disubstituted benzenes and then macro cyclization of the prepared 1,4-disubstituted benzenes. Cyclization was achieved using paraformaldehyde in the presence of Lewis acid catalyst. The desired pillar[5]arenes consisted from five repeating units connected through methylene bridges. Structures of all the pure synthesized 1,4-disubstituted benzenes and pillar[5]arenes were confirmed using 'H, 13C NMR and IR Spectroscopy and mass spectrometry. The tested pillar[5]arenes formed inclusion complexes with different selected guests molecules. The host-guest chemistry were investigated using ESI MS and 'H NMR spectrometry methods.