A simple method for analysis of five local anaesthetics in blood was developed using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry-electron impact ionization selected ion monitoring (GC-MS-EI-SIM). Deuterated lidocaine (d10-lidocaine) was synthesized and used as a desirable internal standard (I.S.). A vial containing a blood sample, 5 M sodium hydroxide and d10-lidocaine (I.S.) was heated at 120 degrees C. The extraction fiber of the SPME system was exposed for 45 min in the headspace of the vial. The compounds adsorbed on the fiber were desorbed by exposing the fiber in the injection port of a GC-MS system. The calibration curves showed linearity in the range of 0.1-20 microg/g for lidocaine and mepivacaine, 0.5-20 microg/g for bupivacaine and 1-20 microg/g for prilocaine in blood. No interfering substances were found, and the time for analysis was 65 min for one sample. In addition, this proposed method was applied to a medico-legal case where the cause of death was suspected to be acute local anaesthetics poisoning. Mepivacaine was detected in the left and right heart blood samples of the victim at concentrations of 18.6 and 15.8 microg/g, respectively.