Two novel long chain multi SO3H-functionlized heteropolyanion-based ionic liquids S4ILs 、S3ILs were synthesized by using aliphatic polyamines, 1,3-propane sultone and Keggin type heteropolyacid as the sources chemicals via quaternarization and acidification two step reaction. Their structures were confirmed by FT-IR, 1H NMP. Two ionic liquids acted as homogeneous catalysts for selective oxidation of benzyl alcohol using 35% H2O2 as oxidant under solvent-free conditions was studied. When the mole ratio of ionic liquids/alcohol/H2O2 =0.05:30:45,the reaction could completed at 70℃ within 4 hour, for S4ILs the corresponding benzaldehydes were obtained in the yields of 81% to 100%. But for S3ILs the corresponding benzoic acids were obtained with yields of 64% to 94%. Two ionic liquids could be easily recovered after removal of water, washed with diethyl ether and drying under vacuum and reused five times without loss in their catalytic activity.