E-commerce adoption by farmers’ cooperatives plays an important role in the digitization and high-quality development of agricultural and rural areas. Based on the integration framework of the technology acceptance model (TAM) and the technology-organization-environment model (TOE), this paper uses the survey data of farmers’ cooperatives in Anhui Province and the Heckman model to analyze the factors influencing the selection and adoption degree of farmers’ cooperatives’ e-commerce adoption and discusses their promotion path. Results show that the probability of e-commerce adoption by cooperatives needs to be improved. Only 24% of cooperatives choose e-commerce adoption, and the average degree of e-commerce adoption is 33.8%. Among the technical factors, perceived usefulness and perceived ease of use imposes significant positive influences on the selection and degree of adoption of cooperative e-commerce, while perceived risk imposed significant negative influences on the selection and degree of adoption of cooperative e-commerce. Among the organizational factors, only land scale and high-level support have significant positive impacts on the adoption of cooperative e-commerce, while industry type has a significant positive impact on the adoption degree of cooperative e-commerce. Among the environmental factors, cooperator support has a significant positive impact on cooperative e-commerce adoption choice and adoption degree, while government support has no significant impacts. Accordingly, to promote the digital transformation and e-commerce transformation of cooperatives, this paper suggests to construct a three-level e-commerce technology application and promotion system of “popularity-consumption-guarantee”, a cooperative talent training system combining “introduction and education”, and an external environment guarantee system of “facility construction - platform construction - policy support”.