An LTQ Orbitrap XL hybrid mass spectrometry method was developed for the determination of illicit drugs and their metabolites, including amphetamine (AP), methamphetamine (MA), dimethylamphetamine (DMA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), ketamine (KET), norketamine (NK), cocaine (COC) and benzoylecgonine (BE), in hair. Micropulverized extraction was employed for sample preparation using a small hair sample (2 cm piece or 0.2 mg). Recoveries of the analytes during sample preparation were estimated using fortified hair samples and ranged from 35.5% for COC to 71.7% for AP. High resolution full-scan mass spectra and unit resolution product-ion spectra were obtained with the Orbitrap analyzer and the linear ion-trap analyzer, respectively. High-resolution extracted ion chromatograms at a tolerance of 3 ppm were utilized for quantification. The analytes were identified using the product-ion spectra in combination with the accurate masses of the corresponding protonated molecules observed in the high-resolution mass spectra. Lower limits of quantification obtained from a 0.2 mg hair sample were 0.050 ng mg−1 (MDMA, KET and BE), 0.10 ng mg−1 (AP, MA, DMA, NK and COC) and 0.50 ng mg−1 (MDA). Two reference materials were analyzed for verification, and segmental analysis of single strands of hair specimens from actual cases was performed.