Objectives: The purpose of this study was to identify the major volatile organic compounds generated during extrusion work with nylon 66 resin and evaluate causes of discomfort among extrusion workers. Methods: A thermal decomposition experiment using nylon 66 resin collected at a worksite was conducted in the laboratory. Based on hazards identified through the thermal decomposition experiment, the exposure levels of the workers were evaluated. Results: The major decomposition products were formaldehyde, acetaldehyde, aniline, cyclopentanone and diphenyl amine. These materials were identical to those sampled in the extrusion booth. The sources of the annoying smells, about which the workers had complained, were formaldehyde, aniline, diphenyl amine, and other hazards in the vapor and fine particles produced by the extrusion work. Formaldehyde, acetaldehyde, and aniline were detected from air samples among workers involved in extrusion work. However, the concentration levels were much lower than Korean occupational exposure limits. The average concentration levels of formaldehyde, acetaldehyde, and aniline were 0.0120 ppm, 0.0036 ppm and 0.0006 ppm, respectively. Conclusions: The extrusion process at around $300^{circ}C$ thermally decomposes the nylon 66 resin, emitting formaldehyde, aniline, and other hazards, which might have made workers uncomfortable due to their smells. The workers exposure levels to volatile organic compounds were far lower than Korean occupational exposure limits. However, since formaldehyde is a human carcinogen and acetaldehyde and aniline are also confirmed animal carcinogens, it is recommended that exposure levels should be maintained at a minimum level.