Porous liquids with chemical separation properties are quite well-studied in general, but there is only a handful of reports in the context of identification and separation of non-gaseous molecules. Herein, we report a Type II porous ionic liquid composed of coordination cages that exhibits exceptional selectivity towards l-tryptophan (l-Trp) over other aromatic amino acids. A previously known class of anionic organic–inorganic hybrid doughnut-like cage (HD) is dissolved in trihexyltetradecylphosphonium chloride (THTP_Cl). The resulting liquid, HD/THTP_Cl, is thereby composed of common components, facile to prepare, and exhibit room temperature fluidity. The permanent porosity is manifested by the high-pressure isotherm for CH4 and modeling studies. With evidence from time-dependent amino acid uptake, competitive extraction studies and molecular dynamic simulations, HD/THTP_Cl exhibit better selectivity towards l-Trp than other solid state sorbents, and we attribute it to not only the intrinsic porosity of HD but also the host-guest interactions between HD and l-Trp. Specifically, each HD unit is filled with nearly 5 l-Trp molecules, which is higher than the l-Trp occupation in the structure unit of other benchmark metal-organic frameworks.