Hair analysis is a useful complement to blood and urine analysis in forensic science, but current procedures are tedious and time consuming. Owing to the difficulty of having a sufficient amount of hair in order to perform the optimization of the extraction method, standard hair was made and the procedure is described. The spiking method is reproducible and linearity can be obtained. Subcritical fluid extraction of opiates from standard and drug addicts' hair was optimized (extraction phase composition, extraction time, etc.) and compared with other extraction techniques (basic and acid hydrolysis, organic solvent and enzymatic digestion) followed by solid-phase extraction. Recovery, coefficient of variation, linearity, detection limits and quantification limits for the subcritical fluid extraction of opiates in hair are described.