Occupational exposures to aromatic hydrocarbons may be overwhelmed by mainstream and secondary smoking exposures. The objective of this study was to evaluate the influence of occupational exposures and smoking on benzene and toluene urinary metabolites. The metabolites were measured in pre and post-work shift urine specimens in oil refinery workers by gas chromatography/mass spectrometry techniques. Post-shift concentration differences between non-smokers and smokers were statistically significant (at p-value <0.05). Pre- and post-shift concentrations of urinary phenol (benzene biomarker) did not vary significantly for both non-smokers and smokers. Occupational exposures to toluene triggered an increase of post-shift levels (compared to pre-shift levels) of urinary cresol for non-smokers and workers who had less than 10 cigarettes during the work shift. For these groups, non-occupational exposures before and during the work shift did not vary. For smokers who did not smoke during the work shift and for those who had more than ten cigarettes during the shift, the post-shift levels of both cresol and hippuric acid were reduced approximately 30% lower than pre-shift levels. This is due to increased exposures to tobacco smoke before the work shift. The relationships between phenol and (cresol + hippuric acid) levels for non-smokers and smokers indicated that elevated co-exposures due to smoking result in the reduction of all metabolites levels in urine. These findings demonstrated that exposures to tobacco smoke may stochastically interfere with occupational exposures when biological monitoring is used to assess occupational health risks. Factors influencing the magnitude of the interference were specimen collection time (in relation to the timing of occupational exposures and excretion rates of biomarkers), smoking intensity and timing before and during the work shift. © 2012 Springer-Verlag.