Theoretically predicted effect of odd-even pattern of electron pairing on behavior of gold clusters in polyaniline/Au-N (N = 0 to 8) has been confirmed experimentally. In these composites the atomic Au clusters with even number of atoms exhibit higher catalytic activity for electrochemical oxidation of n-propanol in 1 M NaOH than the odd-number atoms clusters. Also, infrared spectroscopy shows that even numbered PANI/AuN composites affect the N-H stretching vibration more strongly than the corresponding odd numbered ones. This behavior matches the theoretically predicted variations of HOMO-LUMO gap energy and the stability of the atomic Au clusters. It also agrees with the earlier experimental work in which the UPS spectra of isolated, mass-selected Au clusters have been reported. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.053203jes] All rights reserved.