Two supermolecular adducts involving p-cyclodextrin(β-CD) and long carbonchain alkyl (aqua) cobaltoximes (R= C6H13 and C8H17 ) have been synthesized for the firsttime and characterized by elementary analysis, UV-Vis and H NMR. We used the cyclicvoltammetry methods to characterize the electrochemical behaviour of the inclusion process.In addition, their formation constant Ka was quantitatively determined by using UV-Vismethods. It has been shown that the longer the carbon chain of the alkyl groups are, themore stable the inclusion complexes are. furthermore, by adding n-C8H17Co (DH)2H2O/β-CDto the aqueous solution, it has been found that the formation constant decreased.