A series of sulfonic acid functionalized Br?nsted/Lewis double acdic heteropoly acid based ionic hybrids were synthesized using double sulfonic acid functionalized quarter amunium organic cation, transition metal ions and Keggin type H4SiW12O40、H3PW12O40 as construction unit via molecular self-assembly in water. These compounds acted as catalysts in synthesis of acetal/ketal fragrancy were studied, and founded that the mole ration of ionic hybrid:keton/aldehyde or phenylethyl alcohol :diol or aectal is 0.012:1:1.5, under reflux condition until to no water or alcohol production, a series of benzaldehyde acetal, cyclohexanone ketal, fructone,fraistone and hyacinth body were obtained with yield of 80-99% re-spectively. Ionic hybrid could be recovered and reused by simple filtration, there are no significant decline in yield activity after recycling for 5 times.