Exposure to isocyanates has consistently been reported as the most common cause of occupational asthma. The objectives of this study were to assess how many Australian workers are currently exposed to isocyanates, identify the occupations with highest proportion of exposed workers and identify the main circumstances of exposures. Data comes from the Australian Workplace Exposure Study-Asthma, a national telephone survey which explored the prevalence of current occupational exposure to 227 asthmagens, grouped into 27 groups, among current Australian workers aged 18–65 years. A web-based tool, OccIDEAS, was used to collect job task information and to assign exposure to asthmagens, including isocyanates. Of the 4,878 eligible participants, 2.5% of them were deemed to be probably exposed to isocyanates at work in their current job (extrapolated to 3.0% of the Australian working population). The majority of those exposed were males (90.8%). The most common tasks undertaken that led to these exposures were using expanding foam fillers/sprays and isocyanate and/or polyurethane paints. Exposure occurred mainly among construction workers, wood workers, and painters or printers. This study investigating occupational exposure to isocyanates in a national working population provides information that can be used to inform the direction of occupational interventions and policies to decrease occupational asthma.