In this study, 38 residents of the Jeonnam areas in Korea were assessed for their level of exposure to VOCs. The aim was to understand the difference in levels of indoor, outdoor, and personal exposure to VOCs (benzene, toluene, ethylbenzene) and a health effect assessment was conducted to determine whether there was any fatal cause from carcinogenic or non-carcinogenic elements from case and control group. Personal exposure to benzene showed a higher distribution than indoor and outdoor concentrations, and it was found that the average concentration of the case group was higher than that of the control group in all indoor, outdoor, and personal exposures. With regard to benzene, in the CTE, RME, and Monte-Carlo analysis, all subjects in the case group were seen to exceed the lifetime cancer risk of 10−6 defined by the US EPA and in the RME analysis the control group subjects were also seen to exceed the lifetime cancer risk of 10−6 defined by the US EPA. In the case of toluene, ethylbenzene on the CTE, RME, and Monte-Carlo analysis, the non-carcinogenic standard of 1 was not exceeded.