Two straight chain multi SO3H-functionlized Keggin-type heteropolyacid ionic hybrids (HPAILs-1-2) were synthesized by using aliphatic polyamines, 1,4-butane-sultone and Keggin type heteropolyacid as the sources chemicals via quaternarization and acidification two step reaction。Their structure were confirmed by FT-IR,1H NMP and XRD.HPAILs-1-2 acted as heterogeneous catalysts for oxidation of cyclohexanones using 35% H2O2 as oxidant under solvent-free conditions was studied. Upon the optimized conditions，when the mole ratio of HPAILs-1-2/cyclohexanone/H2O2 =0.05:1:2.5,the reaction could completed at 50℃ within 3 hour and gave ε-caprolactone in the isolated yields of 75% and 70%. HPAILs-1-2 could be easily recovered after filtration, washed with water, diethyl ether and drying under vacuum and reused five times without significant loss in their catalytic activity.