Uptake and support of sustainable technologies that decrease greenhouse gas emissions are critical to mitigating climate change. Engagement in individual (e.g., eating less meat, electric car use) and collective (e.g., petition signing, donating money to environmental causes) sustainability behaviors may correlate with psychological factors including emotions, worry about climate change and natural hazards, and response efficacy. However, little research has explored these relationships in representative samples at high risk for climate-related hazard exposures (e.g., hurricanes, heatwaves, flooding). We assessed climate change-related sustainability behaviors in an ongoing, probability-based representative survey of 1479 Texas and Florida residents repeatedly exposed to climate-related hazards including hurricanes, heatwaves, flooding, and tornadoes. Controlling for demographics, behavior-related positive and negative emotions correlated with engagement in performing a greater number of collective-level sustainability behaviors (positive emotions: IRR = 2.06, p < .001; negative emotions: IRR = 1.46, p = .030). However, negative emotions were mediated by natural hazard worry, which in turn was mediated by climate change worry. Positive emotions were mediated by response efficacy. Individual-level sustainability behaviors were associated with positive emotions (IRR = 1.18, p < .001), which were again mediated by response efficacy. In adjusted analyses unpacking the relationship between discrete emotions and sustainability behaviors, hope was associated with individual- and collective-level sustainability behaviors (all ps < .05). Results suggest general climate change worry may be adaptive and that feelings of hope, relative to other emotions (both positive and negative), may help encourage sustainability behaviors that address climate change. Scalable interventions should explore leveraging these psychological experiences to promote uptake of sustainable technology-related behaviors more broadly.