Bullying at work is a long-standing area of research interest that requires investigation of the role of the individual exposed to systematic negative behaviour. Studies using cross-sectional samples and broad personality measures have found some distinguishing personal characteristics of employees who are bullied compared to others. Few, however have applied theoretical frameworks to explain why personality can play a part in why an individual ends up at the receiving end of bullying and harassment at work. This article applies an overall and specific theoretical model, the vulnerability thesis, to investigating the role of temperament in relation to workplace bullying. The results show that (1) some employees exposed to bullying at work also acted as perpetrators (provocative victims), that (2) exposure to bullying at work is connected with temperamental emotional vulnerability, and that (3) hostility and self-oriented aggression mediate the role of personality in the form of temperament in relation to workplace bullying. Strengths and weaknesses and potential practical implications for helpers of employees exposed to bullying at work are discussed.