Background: Occupational studies on N-N-dimethylformamide (DMF) exposure among migrant workers in Korea are scarce. We determined the urine concentration of N-methylformamide (NMF) among migrant workers with DMF exposure and compared the data with those of native workers. Methods: Data were collected from Workers’ Special Health Examination and Work Environment Monitoring databases during 2014–2019. Workers aged ≥20 years were eligible to participate in the special health examination for DMF exposure. Urine concentrations of NMF were determined and compared between migrant and native workers. We also evaluated the factors affecting the difference in the urine concentration of NMF between the migrant and native workers. Multiple logistic regression was performed by adding confounders step by step. Results: Among 9259 subjects, 504 (5.2%) were migrant workers. The mean urinary concentration of NMF was 6.73 mg/L in migrant workers, which was significantly higher than that in native workers (2.06 mg/L, p < 0.001). The odds of a urine concentration of NMF > 30 mg/L were significantly higher in migrant workers than in native workers after adjusting for sex and age (odds ratio [OR] = 7.31, 95% confidence interval [CI] = 4.66–11.45). However, the odds between the native and migrant workers were not significantly different when fully adjusted for confounders (OR = 1.12, 95% CI = 0.65–1.94). Conclusions: The excessive exposure to DMF among migrant workers was attributed not to differences in biological characteristics but to their work environment. Workers must have awareness of the use of protective equipment and knowledge of hazardous chemicals that they may be exposed to, especially at the workplace.