Abstract: Digitally empowering farmers to adopt organic agriculture technology is an important measure for realizing green and digital synergy in agriculture. Based on the digital literacy and technology adoption theory, this study analyzed the impact of farmers’ digital literacy on their organic agriculture technology adoption by constructing a structural equation model based on the extended unified theory of acceptance and use of technology, using survey data of rural households from four counties in the key ecological functional area of western Hunan Province. The results showed that: 1) performance expectancy had the greatest impact on farmers’ organic agricultural technology adoption, with a total effect of 0.254. Digital general literacy, digital application literacy, and digital innovation literacy played a crucial role in farmers’ adoption of organic agriculture technology, with their impact being comparable to that of performance expectations, and their total effects were 0.210, 0.234, and 0.238, respectively. Moreover, the direct impact of digital general literacy and digital application literacy was greater than its indirect impact. 2) There was heterogeneity in the effects of digital literacy on the organic agriculture technology adoption of farmers with different scales. The effects of digital innovation literacy and digital application literacy on the organic agriculture technology adoption of large-scale farmers were more obvious, and the heterogeneity of the effects of digital innovation literacy on the organic agriculture technology adoption behavior of the two groups of farmers was more prominent. Agricultural experience had a significant moderating effect on the relationship between digital literacy and farmers’ adoption of organic agriculture technology. Thus, we proposed policy suggestions of accelerating the construction of digital infrastructure, popularizing the cultivation of digital literacy among farmers, increasing the publicity and promotion of organic agriculture technology, and appropriately tilting the policy toward small-scale and inexperienced farmers. The contributions of this paper are primarily reflected in two aspects: drawing on the technology adoption model and digital literacy theory, and analyzing the driving forces behind farmers’ adoption of organic agriculture technology across dimensions. Additionally, a structural equation model was employed to simultaneously examine the multi-causal, direct, and indirect effects of these factors.