Abstract: The danger factors can be eliminated by reasonable multiple-step pentthylene glycol reduced pressure distillation. Two 1,3-alternate calix4arene-crown-6 derivatives are synthesized through one pot method. The structure of related compounds is identified by melting point, mass spectrum, 1 H NMR and 13 C NMR measurements. The method may be further generalized in the synthesis of other calixcrown ethers.