The concentrations of Ni, Cu, Zn, and Pb in human scalp hair of 281 individuals working in 10 Syrian industrial plants were determined using co-precipitation by ammoniumpyrolidinedithiocarbamate (APDC) method for total reflection X-ray fluorescence (TXRF) analysis. The results were compared to data obtained for a control group consisted of individuals working at the Syrian Atomic Energy Commission and also to data reported in the literature. The results given by the group of workers in battery plant showed that Pb concentration in human scalp hair samples were higher than those for control group, while some abnormal concentrations were obtained for Cu, Zn and Ni in cables, printing and battery plants, respectively. Normal concentrations of these elements were obtained for hair workers in olive oil, power stations, textile, and iron industrial plants. The relationships of Pb-Pb/Ni and Cu-Cu/Ni were plotted with correlation coefficients of 0.9937 and 0.9014, respectively. In general, the results showed that, the workers who were occupationally exposed to battery industrial pollution are at risk, followed by individuals in printing and cables industries, while the rest of workers in other industries are considered occupationally unexposed.