A sensitive and specific procedure is described for the determination of therapeutically relevant concentrations of L-dopa in plasma and plasma ultrafiltrates (free fraction) by high performance liquid chromatography with electrochemical detection. In plasma samples from healthy adult subjects (n = 15) spiked with L-dopa (500 micrograms l-1) the free fraction averaged 76 +/- = 8% (range 61-84%). Free fraction values increased by 38% with increasing plasma concentrations of L-dopa from 100-5000 micrograms 1-1. L-dopa free fraction was not affect by the presence of 3-O-methyl-dopa at concentrations up to 10,000 micrograms l-1.