How to increase volatility?
The important thing is the solvent does not dissolve the substance. Then their vapour pressures sum up and they boil together.

This technique is massively used for obtaining aromatic oily essences from plants, that are mostly insoluble in water.

The destilate usually forms a stable emulsion, that gets extracted by lipophilic volatile solvent, that is later evaporated to got the substance, or a mixture of them.