Objectives Emergency departments (EDs) are a vital part of healthcare systems, at times acting as a gateway to community-based mental health (MH) services. This may be particularly true for veterans of the Royal Canadian Mounted Police who were released prior to 2013 and the Canadian Armed Forces, as these individuals transition from federal to provincial healthcare coverage on release and may use EDs because of delays in obtaining a primary care provider. We aimed to estimate the hazard ratio (HR) of MH-related ED visits between veterans and non-veterans residing in Ontario, Canada: (1) overall; and by (2) sex; and (3) length of service. Methods This retrospective cohort study used administrative healthcare data from 18,837 veterans and 75,348 age-, sex-, geography-, and income-matched non-veterans residing in Ontario, Canada between April 1, 2002, and March 31, 2020. Anderson–Gill regression models were used to estimate the HR of recurrent MH-related ED visits during the period of follow-up. Sex and length of service were used as stratification variables in the models. Results Veterans had a higher adjusted HR (aHR) of MH-related ED visits than non-veterans (aHR, 1.97, 95% CI, 1.70 to 2.29). A stronger effect was observed among females (aHR, 3.29; 95% CI, 1.96 to 5.53) than males (aHR, 1.78; 95% CI, 1.57 to 2.01). Veterans who served for 5–9 years had a higher rate of use than non-veterans (aHR, 3.76; 95% CI, 2.34 to 6.02) while veterans who served for 30+ years had a lower rate compared to non-veterans (aHR, 0.60; 95% CI, 0.42 à 0.84). Conclusions Rates of MH-related ED visits are higher among veterans overall compared to members of the Ontario general population, but usage is influenced by sex and length of service. These findings indicate that certain subpopulations of veterans, including females and those with fewer years of service, may have greater acute mental healthcare needs and/or reduced access to primary mental healthcare.