The self-medication hypothesis may explain the co-morbidity of affective and substance use disorders. Research shows increased prevalence, frequency, and intensity of binge drinking and post-traumatic stress disorder (PTSD) among those directly exposed to the 9/11 terrorist attacks on the World Trade Center (WTC), however, little is known about PTSD symptomology and intentional self-medication with alcohol (ISMA) among this group. We used WTC Health Registry data (N = 28,935) to describe the relationship between ISMA and specific symptom clusters of probable 9/11-related PTSD, the number of PTSD symptom clusters endorsed, and binge drinking intensity. Multivariable logistic regression models were used to estimate the adjusted odds ratios (AORs) and 95% confidence intervals (CI). ISMA was most strongly associated with the hyperarousal PTSD symptom cluster (AOR = 2.04 [1.88, 2.21]) and the endorsement of one (AOR = 1.80 CI [1.65, 1.95]), two (AOR = 2.51 CI [2.28, 2.77]), or three (AOR = 2.84 CI [2.55, 3.17]) PTSD symptom clusters, indicating a clear dose–response relationship. A significant number of 9/11-exposed persons continue to experience PTSD symptoms and engage in ISMA as a potential coping mechanism. Repeated screenings for self-medicative alcohol use among survivors of mass traumas with PTSD symptoms is of public health importance.