Healthcare practitioners’ fitness to practise has often been linked to their personal and demographic characteristics. It is possible that situational factors, such as the work environment and physical or psychological well-being, also have an influence on an individual’s fitness to practise. However, it is unclear how these factors might be linked to behaviours that risk compromising fitness to practise. The aim of this study was to examine the association between job characteristics, well-being and behaviour reflecting risky practice amongst a sample of registered pharmacists in a region of the United Kingdom. Data were obtained from a cross-sectional self-report survey of 517 pharmacists. These data were subjected to principal component analysis and path analysis, with job characteristics (demand, autonomy and feedback) and well-being (distress and perceived competence) as the predictors and behaviour as the outcome variable. Two aspects of behaviour were found: Overloading (taking on more work than one can comfortably manage) and risk taking (working at or beyond boundaries of safe practice). Separate path models including either job characteristics or well-being as independent variables provided a good fit to the data-set. Of the job characteristics, demand had the strongest association with behaviour, while the association between well-being and risky behaviour differed according to the aspect of behaviour being assessed. The findings suggest that, in general terms, situational factors should be considered alongside personal factors when assessing, judging or remediating fitness to practise. They also suggest the presence of different facets to the relationship between job characteristics, well-being and risky behaviour amongst pharmacists.