A reduction in risk of occupational exposure to chemical hazards within the workplace has been the focus of attention both through industry initiatives and legislation. The aims of this study were to develop an exposure matrix by industry and process, and to apply this matrix to control the risk of occupational exposure to Dichloromethane (DCM). The exposure matrix is a tool to convert information on industry and process into information on occupational risk. The exposure matrix comprised industries and processes involving DCM, based on an exposure database provided by KOSHA (the Korean Occupational Safety and Health Agency), which was gathered from a workplace hazards evaluation program in Korea. The risk assessment of the exposure matrix was performed using Hallmark risk assessment tool. The results of the risk assessment were indicated by a Danger Value (DV) calculated from the combination of hazard rating (HR), duration of use rating (DUR), and risk probability rating (RPR) of exposure to the chemical, and were divided into four control bands which were related to control measures. The applicability of the risk assessment of the exposure matrix was evaluated by a field study, and survey of the employees of the exposure matrix groups. Among 45 industries examined, this study found that greater attention should be paid to two industries: the manufacture of other optical instruments and photographic equipment, and the manufacture of printing ink, and to one process among 47 examined, the packing process in the manufacture of printing ink, because these were regarded as carrying the highest risk. This tool of a risk assessment for the exposure matrix can be applied as a general exposure information system for hazard control, risk quantification, setting the occupational exposure limit, and hazard surveillance. The exposure matrix includes workforce data, and it provides information on the numbers of exposed workers in Korea by agent, occupation, and level of exposure and risk.