The main objective of this study was to investigate aluminum, gallium, indium, arsenic, and antimony exposures on blood and urine levels in the optoelectronic workers. One hundred seventy subjects were enrolled in this cohort study. Whole blood and urine levels were determined by inductively coupled plasma-mass spectrometry. Blood indium and urine gallium and arsenic levels in the 103 workers were significantly higher than that in 67 controls during the follow-up period. In regression models, the significant risk factors of exposure were job title, preventive equipment, Quetelet’s index, sex, and education level. The findings of this study suggest that gallium, indium, and arsenic exposure levels may affect their respective levels in blood and urine. The use of clean, preventive equipment is recommended when prioritizing the administration of safety and hygiene in optoelectronics industries.