A receptor for barbiturates, N,N'-Bis-[6-(2-ethylhexanoylamino)-pyridin-2-yl]-isophthalamide, was designed to dissolve in plasticizers of poly(vinyl chloride) (PVC). Microextractions using receptor-doped films of PVC were carried out as a function of receptor concentration. The effect of the concentration of the receptor on extraction yield is considerable for barbiturates that have significant binding to the receptor but negligible for very similar molecules that do not bind to the receptor strongly. Thus, it is the receptor's ability in molecular recognition, not its generic ability as an H-bonding cosolvent, that is important. On the other hand, NMR data show that the receptor self-associates. A simple, approximate analysis is given to extract the amount of active receptor from the data. Receptor-enhanced extractions of barbiturates from urine are compared to extractions using a phosphate ester as solvent.