Asian/Pacific Islander (API) communities in the United States often reside in metropolitan areas with distinct social and environmental attributes. Residence in an ethnic enclave, a socially distinct area, is associated with lower gestational diabetes mellitus (GDM) risk, yet exposure to high levels of air pollution, including volatile organic compounds (VOCS), is associated with increased GDM risk. We examined the joint effects of ethnic enclaves and VOCs to better understand GDM risk among API women, the group with the highest prevalence of GDM. We examined 9069 API births in the Consortium on Safe Labor (19 hospitals, 2002–2008). API ethnic enclaves were defined as areas ≥66th percentile for percent API residents, dissimilarity (geographic dispersal of API and White residents), and isolation (degree that API individuals interact with another API individual). High levels of 14 volatile organic compounds (VOC) were defined as ≥75th percentile. Four joint categories were created for each VOC: Low VOC/Enclave (reference group), Low VOC/No Enclave, High VOC/Enclave, High VOC/No Enclave. GDM was reported in medical records. Hierarchical logistic regression estimated odds ratios (OR) and 95% confidence intervals (95%CI) between joint exposures and GDM, adjusted for maternal factors and area-level poverty. Risk was estimated for 3-months preconception and first trimester exposures. Enclave residence was associated with lower GDM risk regardless of VOC exposure. Preconception benzene exposure was associated with increased risk when women resided outside enclaves [High VOC/No Enclave (OR:3.45, 95%CI:1.77,6.72)], and the effect was somewhat mitigated within enclaves, [High VOC/Enclave (OR:2.07, 95%:1.09,3.94)]. Risks were similar for 12 of 14 VOCs during preconception and 10 of 14 during the first trimester. API residence in non-enclave areas is associated with higher GDM risk, regardless of VOC level. Ethnic enclave residence may mitigate effects of VOC exposure, perhaps due to lower stress levels. The potential benefit of ethnic enclaves warrants further study.