A comprehensive understanding of the reasons for over-fertilization is critical to agro-environment sustainability, especially for the fast-growing farming areas under urbanization. Previous studies are more quantitatively biased and, in most cases, merely focus on demographical, economic, and political factors while excluding in-depth qualitative and holistic investigation. To address this gap, this chapter attempts to construct a conceptual framework to investigate the hidden mechanism of chemical fertilizer overuse through an empirical study in the Dancheng County of China. Such a framework is based on Kollmuss and Agyeman (2002), and Blake’s (1999) works but incorporates demographical factors and external barriers for explaining the awareness-behavior gap. Results indicate that environmental awareness is not necessarily related to chemical fertilizer overuse as the reasons for farmers’ inappropriate behaviors are embedded within an intricate network of economic, social-cultural, and policy-influenced factors incorporating labor and time constraints, risk-averse decisions, intergenerational division, farm size, attachment to instant gratification, land attachment, peer pressure, and distortion of agricultural and land-use policies, which has roots in the agricultural marginalization and urban-rural dichotomy. Based on the results, policy recommendations are provided.