This work presents a comparative evaluation of extraction procedures for the capillary analysis of seven opiates (meperidine, morphine, naloxone, tramadol, fentanyl, sufentanyl, and alfentanyl) in human hair. Pieces of hair (50-150 mg) were subjected to acidic hydrolysis (0.25 mmol L(-1) HCl at 45 degrees C, overnight) followed by pH adjustment and either liquid-liquid extraction (LLE) in hexane, petroleum ether, dichloromethane, and ethyl acetate solvents, or solid-phase extraction (SPE) in octadecyl, cyanopropyl, and aminopropyl bonded silica and cation exchange polymeric phases. Excellent recoveries of approximately 70% (naloxone and fentanyl and its analogues), 88% (meperidine), and ca. 100% (morphine and tramadol) were obtained using SPE in a M-fixed-mode cation exchange reversed-phase cartridge (Oasis MCX LP, Waters Corp., Milford, MA, U.S.A.), making this type of procedure eligible for novel clinical and forensic methodologies for hair analysis. The utility of the proposed extraction technique was demonstrated by the analysis of hair extracts from patients using morphine as part of their pain management protocol.