This paper reports a dimethyl sulfoxide (DMSO) phase offered by a coordination polymer gel that consists of metal ions and a calixarene that has multiple binding sites. This metallogel, virtually 98% of which is DMSO, has high stability in aqueous solution over a wide range of pH (1-13), even at 100 °C, rejects ions (almost) completely, and allows nonionic organic molecules spontaneously enriching into it with high efficiency, up to ∼60 times enrichment from aqueous solution and ∼2000 times enrichment from the gas phase.