This paper characterizes a novel multianalyte competitive binding, electrokinetic capillary-based immunoassay for urinary methadone, opiates, benzoylecgonine (cocaine metabolite) and amphetamines. After incubation of 25 mu l urine with the reactants for several minutes in the presence of an internal standard, a small aliquot of the mixture is applied onto a fused-silica capillary and the unbound fluorescein labelled drug tracers are monitored by capillary electrophoresis with on-column laser induced fluorescence detection. The multianalyte assay is shown to be rapid, simple, quantitative, capable of recognizing urinary drug concentrations greater than or equal to 30 ng/ml and suitable for screening of patient urines. Data are demonstrated to compare well with those obtained by routine screening methods based on enzyme multiplied immunoassay techniques and fluorescence polarization immunoassays. The electrokinetic capillary assay has been validated via analysis of external quality control urines and confirmation analysis of patient urines using GC-MS. (C) 1999 Elsevier Science B.V. All rights reserved.