A procedure for copper and nickel determination in scalp hair by solid sampling electrothermal atomic absorption spectrometric method was described. The hair samples (0.02 to 0.4. mg) were inserted directly on the platforms of solid sampling autosampler. The effects of pyrolysis temperature, atomization temperature, the amount of sample as well as addition of a modifier (Pd/Mg) and/or auxiliary digesting agents (hydrogen peroxide and nitric acid) and/or a surfactant (Triton X-100) on the determination of copper and nickel by solid sampling atomic absorption spectrometry were investigated. After optimization of parameters, the average recoveries of copper in two different certified reference hair samples were 105.7 and 97.6%. The recoveries of nickel in the both certified reference hair samples were in 95.2 and 96.4%. The limits of detection (3σ, N = 10) for copper and nickel were 22. ng/g and 35. ng/g, respectively. Heterogenous distribution of analyte in microscale for segmental analysis could be determined which is important to know that analyte quantity and time of poisoning of a person was exposed. For this purpose, 0.5. cm of pieces were cut along one or a few close strands and analyzed by solid sampling. This process could not be performed by wet-digestion method because 50. mg of sample is needed each time. Finally, the method was applied for the determination of copper and nickel concentrations in the hairs of different persons. © 2011 Elsevier B.V.