It is generally accepted that chemical testing of biologic fluids is the most objective means of diagnosis of drug use. The presence of a drug analyte in a biologic specimen can be used to document exposure. The standard for drug testing in toxicology is an immunoassay screen conducted on a urine sample, followed by confirmation by gas chromatography with mass spectrometric detection. In recent years, remarkable advances in sensitive analytic techniques have enabled the analysis of drugs in unconventional biologic specimens such as saliva or hair. The aim of this review is to document the current status of drugs of abuse testing in saliva and some doping agents in hair. The influence on drug concentration of the procedure of saliva sampling is described. Screening procedures along with specific methods are reviewed for the determination of amphetamines, cannabis, cocaine, and opiates in saliva. Before an extensive review on the detection of anabolics, corticosteroids, and beta-adrenergic stimulants in hair, the place of this specimen in doping control is discussed, with a focus on the potential problems of this new technology.