National key ecological function zones (NKEFZs) in China are critically important to maintain ecological security and accelerate the construction of the ecological civilization system. The quantitative impact of NKEFZs on green development at the county level has not received much attention. In this study, the county-level statistics of the Yanshan–Taihang Mountainous area in Hebei province from 2013 to 2018 were selected as samples. The symbiotic relationship between economy and ecology was measured and development patterns were identified using an improved Lotka–Volterra model. Then, a difference-in-differences (DID) model was used to empirically test the green development effects of establishing NKEFZs, as well as the dynamic changes of the effects and the heterogeneity of different development patterns. The results show that: (1) Green development in the sample area can be classified into four patterns: Low-High, High-Low, High-High, and Low-Low; (2) NKEFZs reduce the level of green development in the study interval and have a persistent negative effect on the level of green development; and (3) NKEFZs have a significant negative effect on areas of Low-High and High-Low development patterns, while the effect on areas of Low-Low development patterns is not significant. Overall, the results indicate that NKEFZs have a negative impact on the green development of the Yanshan–Taihang Mountainous area in Hebei Province. Finally, to promote green development in mountainous areas, the paper makes the following recommendations: Firstly, to improve the transfer payment system for NKEFZs and bring into play a long-term mechanism for the compensation effect of transfer payments. Secondly, to cultivate special industries to achieve the differentiated development of county economies. Thirdly, to accelerate the optimization and adjustment of industrial structures and promote the coordinated development of primary, secondary, and tertiary industries.
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