Feed mill workers may handle or process maize contaminated with aflatoxins (AFs). This condition may lead to an unacceptable intake of toxins deriving from occupational exposure. This study assessed the serological and urinary levels of AFs in workers exposed to potentially contaminated dusts in two mills. From March to April 2014, blood and urine samples were collected, on Monday and Friday morning of the same working week from 29 exposed workers and 30 non-exposed controls. AFs (M1, G2, G1, B1, B2) and aflatoxicol (AFOH) A were analyzed. Each subject filled in a questionnaire to evaluate potential food-borne exposures to mycotoxins. AFs contamination in environmental dust was measured in both plants. No serum sample was found to be positive. Seventy four percent of urine samples (73.7%) revealed AFM1 presence. AFM1 mean concentration was 0.035 and 0.027 ng/mL in exposed and non-exposed workers, respectively (p = 0.432); the concentration was slightly higher in Friday’s than in Monday’s samples, in exposed workers, 0.040 versus (vs.) 0.031 and non-exposed controls (0.030 vs. 0.024, p = 0.437). Environmental AFs contamination ranged from 7.2 to 125.4 µg/kg. The findings of this study reveal the presence of higher AFs concentration in exposed workers than in non-exposed controls, although these differences are to be considered consistent with random fluctuations.