Dibenzoarsacrowns have been synthesized as a novel class of heteroatom-fused crown ethers. The dibenzoarsacrowns can size-selectively capture alkali metal cations, and the arsenic atoms chemoselectively coordinated to gold(i) chloride (AuCl) due to the soft Lewis acid-base interaction. It is notable that the AuCl complex of 21-dibenzoarsacrown-7 further encapsulated Na+ with the enhanced association constant from bare 21-dibenzoarsacrown-7. The positive allosteric effect was studied computationally.