Molecular assemblies in α and β-cyclodextrin with most important anticonvulsant drug sodium valproate in aqueous medium and solid phases have been explored by reliable spectroscopic and physicochemical techniques as potentially important controlled drug delivery systems. Host–guest inclusion complexes of 1:1 stoichiometry have been determined by surface tension, conductivity studies and inclusion phenomena was confirmed by 1H NMR, FT-IR studies. The results indicated a higher degree of encapsulation in the case of α-cyclodextrin than that in β-cyclodextrin. The formation of the inclusion complexes was elucidated by hydrophobic effects, structural effects, electrostatic forces and H-bonding interactions.