Rural women in developing nations are especially vulnerable to higher health risks due to environmental pollution exposure and are more likely to experience poorer health outcomes. Using data from the 2013 China General Social Survey CGSS2013, this study empirically examined the relationship among environmental knowledge (EK), pollution, health investment (i.e., holding and purchasing a public health insurance policy, engaging in frequent physical activity, and acquiring commercial insurance), and health status. The sample was composed of 1930 women residing in rural regions in China. Three main research questions are investigated: whether environmental knowledge affects health investment and health status, whether health investments impact health status, and whether the relationship between environmental knowledge and health status is mediated by health investment. Our results showed that the level of EK for women in rural China significantly impacted their self-reported physical and mental health. To account for potential endogeneity due to mutual causality, this study employed television usage and network usage as two instrumental variables (IVs) of EK and used an IV-probit method. Additionally, we estimated a model that replaced health status with the variable Body Mass Index (BMI) to assess the reliability and robustness of our results. The results were consistent, providing evidence of robustness. Additionally, we examined the relationship between health investment (holding and purchasing a public health insurance policy, engaging in frequent physical activity, and acquiring commercial insurance) and health status. Our results indicated that the level of EK had no significant impact on participating in the new rural cooperative medical system. However, the preference for purchasing commercial insurance was positively impacted by EK, though it did not directly affect health status. Conversely, an increase in EK and pollution was associated with a greater likelihood of engaging in physical exercise, which, in turn, improved overall mental health.