The synergistic interaction between emergency management departments and enterprises constitutes a fundamental mechanism for mitigating the risks of technological accidents caused by natural disasters (Natech). The efficacy of this collaborative approach is impacted by comprehensive risk analyses and the game between government and enterprise. Predicated on these premises, the evolutionary game analysis of government–enterprise collaboration in coping with Natech risk was carried out. Firstly, an evolutionary game model of government–enterprise collaboration in coping with Natech risk was constructed. Secondly, the evolutionary stability strategy (ESS) was developed. Finally, these strategies were substantiated through numerical simulations. The findings revealed that at lower levels of Natech risk, enterprises will choose low investment in coping capacity building, and emergency management departments will choose delayed disposal. Under moderate Natech risk, enterprises will increase their investments if emergency management departments persist with delayed strategies, and emergency management departments will react proactively if enterprises persist with low investment. Under a high Natech risk, a pattern of strategic misalignment emerges between the two entities. This study contributes a theoretical basis for the optimization of government–enterprise collaboration in coping with Natech risks.