Decision-making processes used by experts when undertaking occupational exposure assessment are relatively unknown, but it is often assumed that there is a common underlying method that experts employ. However, differences in training and experience of assessors make it unlikely that one general method for expert assessment would exist. Therefore, there are concerns about formalizing, validating, and comparing expert estimates within and between studies that are difficult, if not impossible, to characterize. Heuristics on the other hand (the processes involved in decision making) have been extensively studied. Heuristics are deployed by everyone as short-cuts to make the often complex process of decision-making simpler, quicker, and less burdensome. Experts' assessments are often subject to various simplifying heuristics as a way to reach a decision in the absence of sufficient data. Therefore, investigating the underlying heuristics or decision-making processes involved may help to shed light on the 'black box' of exposure assessment.A mixed method study was conducted utilizing both a web-based exposure assessment exercise incorporating quantitative and semiqualitative elements of data collection, and qualitative semi-structured interviews with exposure assessors. Qualitative data were analyzed using thematic analysis.Twenty-five experts completed the web-based exposure assessment exercise and 8 of these 25 were randomly selected to participate in the follow-up interview. Familiar key themes relating to the exposure assessment exercise emerged; 'intensity'; 'probability'; 'agent'; 'process'; and 'duration' of exposure. However, an important aspect of the detailed follow-up interviews revealed a lack of structure and order with which participants described their decision making. Participants mostly described some form of an iterative process, heavily relying on the anchoring and adjustment heuristic, which differed between experts.In spite of having undertaken comparable training (in occupational hygiene or exposure assessment), experts use different methods to assess exposure. Decision making appears to be an iterative process with heavy reliance on the key heuristic of anchoring and adjustment. Using multiple experts to assess exposure while providing some form of anchoring scenario to build from, and additional training in understanding the impact of simple heuristics on the process of decision making, is likely to produce a more methodical approach to assessment; thereby improving consistency and transparency in expert exposure assessment.