In this study, a series of eight 3-oxapentane podand derivatives was successfully prepared using the croton condensation reaction of 1,5-bis(aryl)-1,5-dithia-3-dioxadecane and 1,5- bis(aryl)-1,3,5-trioxadecane with bezaldehyde or acetophenone derivatives in acidic condition. These synthesized derivatives have the structure of acyclic crown rings inserted by polyether or polythioether chain and vinyl ketone chain conjugated with an aryl group. Therefore, they are important sources for “host-guest” chemistry. They can wrap around central alkali metal cations as well as organic cations and anions or even molecules to make interesting ion pair receptors. Moreover, the structure of new podands was also determined by spectral analyses including IR, 1H NMR, MS spectrocopies.