The possibility of acute hepatotoxicity caused by dimethylformamide (DMF) requires regular monitoring of the workers who are using DMF to prevent the occupational disease. The authors performed ambient and biological monitoring of workers involved in synthetic leather manufacturing processes using DMF to assess the correlation between the markers of ambient and biological monitoring of DMF. The authors monitored 142 workers occupationally exposed to DMF from 19 workshops in the synthetic leather and ink manufacturing industries located in northern region of Gyeonggi-do. The subjects answered questionnaire on work procedure and use of personal protective equipment to be classified by exposure type. DMF in air samples collected using personal air samplers, diffusive and active sampler, was analysed using gas chromatograph-flame ionization detector (GC-FID) with DB-FFAP column (length 30 m, i.d. 0.25 mm, film thickness 0.25 ${mu}m$). Urinary N-methylformamide (NMF) was analysed using gas chromatograph-mass selective detector (GC-MSD) at selected ion monitoring (SIM) mode with DB-624 column (length 60 m, i.d. 0.25 mm, film thickness 1.40 ${mu}m$). Geometric mean (GM) and geometric standard deviation (GSD) of the ambient DMF was $6.85{pm}3.43$ ppm, and GM and GSD of urinary NMF was $42.3{pm}2.7$ mg/L. The ratio of subjects with DMF level over 10 ppm was 44%, and those with urinary NMF over 15 mg/L was 87%. NMF in urine adjusted by DMF in air was $4.61{pm}2.57$ mg/L/ppm and $9.50{pm}2.41$ mg/L/ppm, respectively, with or without respirator. There was seasonal differences of NMF in urine adjusted by DMF in air, $7.63{pm}2.74$ mg/L/ppm in summer and $4.53{pm}2.29$ mg/L/ppm in winter. The urinary NMF concentration which corresponds to 10 ppm of ambient DMF was 52.7 mg/L (r=0.650, n=128). Considering the difference of the route of exposure which resulted from the compliance of wearing personal protective equipment, the estimated contribution of respiratory and dermal exposure route for DMF was 48.5% vs. 51.5%.