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Aims: Errors with prescribing high‐risk medicines (HRMs) have a greater propensity to cause harm than with non‐HRMs. Prescribing errors arise due to multiple factors and it can be particularly challenging for junior doctors to prescribe safely during the on‐call period. Knowledge regarding the challenges of prescribing HRM during the on‐call period would be useful to target preventative interventions. The aim of this study was to explore the challenges encountered by foundation doctors (doctors who have graduated medical school within the last 2 years) when prescribing specific HRMs (anticoagulants, insulin and opioids) safely during the on‐call period. Methods: Six focus groups exploring the challenges of prescribing HRMs safely during the on‐call period were conducted, 3 with foundation year 1 and 3 with foundation year 2 doctors from across 3 different hospitals. A thematic framework analysis based on the London Protocol was conducted. Results: Doctors described multiple challenges to prescribing HRMs safely during the on‐call period including a lack of prescribing support, nursing pressure, complex prescribing tasks, unknown patients as well as individual factors such as lack of knowledge and tiredness. Many of these factors exist to some extent during the day, yet the nature of the on‐call period as a fast‐paced environment heightened the challenges that prescribers faced. Conclusion: There are multiple challenges experienced by foundation doctors when prescribing HRMs during the on‐call period. The potentially devastating consequences of errors with HRMs means that closer attention and more concern from healthcare professionals, researchers and policymakers is required to improve safe prescribing of HRMs in hospitals. [ABSTRACT FROM AUTHOR]