Background: The British Police Service and Armed Forces are male-dominated occupations, characterised by frequent trauma exposure and intensive demands. Female police employees and military personnel may have unique experiences and face additional strains to their male counterparts. This analysis compared the levels of post-traumatic stress disorder (PTSD), hazardous/harmful alcohol consumption, and comorbidity in female police employees and military personnel. Methods: Police data were obtained from the Airwave Health Monitoring Study (N = 14,145; 2007–2015) and military data from the Health and Wellbeing Cohort Study (N = 928; phase 2: 2007–2009 and phase 3: 2014–2016). Multinomial/logistic regressions analysed sample differences in probable PTSD, hazardous (14–35 units per week) and harmful (35 + units per week) alcohol consumption, and comorbid problems. We compared covariate adjustment and entropy balancing (reweighting method controlling for the same covariates) approaches. Results: There were no significant differences in probable PTSD (police: 3.74% vs military: 4.47%) or hazardous drinking (police: 19.20% vs military: 16.32%). Female military personnel showed significantly higher levels of harmful drinking (4.71%) than police employees (2.42%; Adjusted Odds Ratios [AOR] = 2.26, 95% Confidence Intervals [CIs] = 1.60–3.21), and comorbidity (1.87%) than police employees (1.00%, AOR = 2.07, 95% CI = 1.21–3.54). Entropy balancing and covariate-adjustments obtained the same results. Conclusions: Comparable levels of probable PTSD were observed, which are slightly lower than estimates observed in the female general population. Future research should explore the reasons for this. However, female military personnel showed higher levels of harmful drinking than police employees, emphasising the need for alcohol interventions in military settings.