This study reports the results obtained with the environmental and biological monitoring of 34 workers exposed to acrylonitrile (ACN). Occupational exposure was monitored during 8-h work shifts with both active and diffusive personal samplers which yielded comparable results. The median exposure was 78 micrograms/m3. The ACN concentration in urine collected at the end of the work shifts correlated significantly with the environmental exposure. The ACN concentration in the pre-shift urine samples (median 3.6 micrograms/l) was lower than that found in the post-shift samples (median 10.9 micrograms/l), but higher than in the urine of non-exposed people (median 0.45 microgram/l). Smoking is an important confounding factor in monitoring exposure to ACN. The ACN concentration in urine provides reliable information about occupational and non-occupational exposure to ACN. Aspects of the mechanism of ACN excretion in urine are also discussed.