Introduction: Post-traumatic stress disorder (PTSD) and extra-medical opioid Use (EMOU) frequently co-occur. Few studies have examined the relationship between EMOU and social networks among people with PTSD. Accordingly, this study examined social networks in a sample of people with PTSD in the United States by assessing the association between social network size/diversity and lifetime EMOU status. Methods: Data came from a cross-sectional, nationally representative sample of adults who participated in the National Epidemiologic Survey on Alcohol and Related Conditions-III (NESARC-III) from 2012 to 2013. For people with past-year PTSD (unweighted n = 1,764), social network size and diversity were estimated by lifetime EMOU status. Multivariable logistic regression models examined the association between social network size, diversity, and EMOU adjusting for sociodemographics, cigarette use, major depression, and anxiety disorder. Results: Between 2012–2013, 24% of people with PTSD had lifetime EMOU. Those with EMOU had a lower social network size and diversity than individuals without EMOU (14 vs. 17 persons, 4 vs. 5 groups, p-values < 0.05). In adjusted models, EMOU was significantly associated with social network diversity (AOR = 0.91; 95% CI: 0.82, 0.99), but not with social network size (AOR = 1.00; 95% CI: 0.98, 1.01). Conclusions: Less diverse social networks were associated with lifetime EMOU among people with PTSD. Future research should examine associations between the quality of social networks and EMOU, ideally from longitudinal studies.