Background: Acute poisonings are common presentations to emergency departments (EDs) worldwide and require rapid assessment. Consultant emergency physicians (EPs) faced with various toxicological presentations must initiate rapid investigations and empirical management. This study aimed to determine emergency department doctors’ level of knowledge and confidence in toxicological presentations, and factors that predicted these outcomes. Methods: Target participants included members of the Australasian College for Emergency Medicine (ACEM) and readers of the emergency medicine website, “Life in the Fast Lane”. The survey was distributed electronically via the ACEM bulletin and posted on Life in the Fast Lane. A survey was designed based on toxicology multiple choice questions (MCQs). The questionnaire comprised 59 items: 10 demographic items; 20 items about confidence; 28 MCQs assessing knowledge of common and serious toxicological presentations. Results: There were 467 consenting respondents from 31 countries, with most residing in Australia (306/467, 66%). Respondents comprised similar proportions of consultant emergency physicians (196/467, 42.0%), and trainees (197/467, 42.2%).  Almost two-thirds (292/467; 62.1%) had received formal training in toxicological emergencies, while a third (166/467, 35.5%) had participated in a relevant conference or workshop. A total of 284/339 (83.8%) participants completing all items achieved a knowledge test score >50%. More than 65% incorrectly answered questions on pharmacology of serotonin syndrome and lithium toxicity, and more than half incorrectly answered questions on use of 12 lead ECG in toxicology, calcium channel antagonist or tricyclic antidepressant toxicities. Predictors of overall knowledge for toxicology were receipt of formal toxicology education, and clinicians’ experience and seniority. Conclusion: The knowledge and confidence of doctors working in emergency departments is varied, yet correlated. Emergency medicine training programs should consider the benefit of reviewing current toxicological education, including the provision of further educational support to regional and rural hospitals.