Presently, disulfiram is used in aversion therapy for recovering alcoholics. It acts by inhibiting aldehyde dehydrogenase, leading to high blood levels of acetaldehyde. A simple direct injection micellar liquid chromatographic procedure was developed to determine disulfiram in illicit preparations (ayurvedic, herbal, divine ash, and traditional medicine), as well as in pharmaceuticals and biological samples (urine). After application of a predictive optimization strategy, the proposed method was developed using a 0.1 M sodium dodecyl sulfate-butanol 4% (v/v) buffered to pH 7 as the mobile phase at a flow rate of 1 mL/min, an octyl silyl (C8) 150 mm column, and diode array detection at 248 nm. Under the above conditions, the analysis time was below 8 min. Validation studies were based on U.S. Food and Drug Administration guidelines. The LOD (3 x SD criterion) was 15 ng/mL and LOQ (10 x SD criterion) was 70 ng/mL for disulfiram. The intraday and interday precisions were below 3.5%, recoveries were in the range of 97-102%, and robustness was below 3%. The optimized and validated micellar liquid chromatographic method was successfully applied to the determination of disulfiram in ayurvedic, herbal, divine ash, and other samples. The procedure developed could also be used in the fields of QC, routine analysis, and pharmacokinetic studies.