Adsorption of n-alkanes (C-5-C-10), isooctane, benzene, toluene and p-xylene on MOF-5 was studied by means of quasi-equilibrated temperature programmed desorption and adsorption (QE-TPDA) and temperature programmed desorption (TPD). Unusual thermodesorption profiles showing increasing complexity with the size of a probe molecule have been observed. Number of peaks in the thermodesorption profile increased from one for pentane or benzene to five for decane. Considerable adsorption desorption hysteresis was found for isooctane. These unusual thermodesorption profiles were discussed in comparison to those obtained for zeolites and ordered mesoporous silicas. (C) 2014 Elsevier B.V. All rights reserved.