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Nowadays, there is a growing interest in pro-environmental foods produced by pro-environmental practices. However, consumers’ payment motivations towards such foods are currently poorly understood. This manuscript provided a critical investigation of Chinese consumers’ intention to pay a premium (ITPP) for rice grown with green manure as crop fertilizer (GMR). One focus was the establishment of an explanatory structural research framework that includes effects of environmental behavior spillover (EBS) and public information induction (PII), another focus was to analyze the impacts of the selected structural elements on ITPP by introducing education as a moderator. Results suggest that consumers’ ITPP can be largely influenced by PII, therefore, for GMR marketers and policy makers, measures should be developed to widen consumers’ access to public information related to GMR and to improve their capacity of screening effective information. EBS, when ITPP remains low, emerged as a pivotal predictor of consumers’ ITPP. This observation provides us with the enlightenment that breeding consumers’ daily environmental behaviors is highly valued to inspire their payment intention in the early stages of GMR market development. Another finding is that, with the introduction of the educational variable, the influence coefficients of EBS and PII on ITPP increased from 0.42 and 0.53 to 0.61 and 0.66, respectively, which means that it is possible to boost consumers’ payment intention by improving their educational attainment. This study contributes to the existing literature by providing empirical evidence for the GMR industrial upgrading strategy and have significant implications for the environmental governance of the agricultural sector.