The organic food industry in China has been developing fast with the increasing consumer demand for healthier, safer, and more nutritious foods since the epidemic outbreak. It is of great significance to understand the psychological preference of consumers for organic food and adjust the marketing strategy accordingly. In this study, we adopted the multi-group structural equation model (SEM) to analyze 571 questionnaire data and explored the effects of consumers’ perception on the sensory appeal of organic food, perception on promotional stimulation, positive emotion, and perceived social value on the purchase intention of organic food. Based on the Stimulus–Organism–Response (S-O-R) model, this study divides the route affecting organic consumption behavior into the rational route and emotional route. It was proved that the emotional route (positive emotion) has a greater impact on the purchase intention of organic food than the rational route (perceived social value). In addition, there are different purchase intentions among different product types. Specifically, compared with organic tea, positive emotion has a greater effect on the purchase intention for organic rice. This study provides an important reference for the organic food-marketing strategy of enterprises.