In the era of Industry 5.0, innovation in blockchain technology is expected to have a significant impact on energy efficiency and carbon emissions, especially in hybrid energy systems. This paper has obtained the innovation data on the blockchain patent of listed companies in China from 2010 to 2022 by machine learning and text analysis methodology of large language model. On this basis, the relationship between the enterprises’ blockchain technology innovation and the intensity of fossil energy consumption has been discussed. The study found that (1) the enterprises’ blockchain technology innovation is able to reduce the intensity of fossil energy consumption, and this conclusion remains valid via controlling for endogeneity and upon the completion of robustness test. (2) In terms of the mechanism, the enterprises’ blockchain technology innovation can achieve energy transition by reducing the cost of internal control, strengthening external supervision, improving the efficiency of resource allocation and strengthening the channels of supply chain management. (3) Further research has found that the energy effects as a result of blockchain technology innovation help to improve operational efficiency and lower the level of carbon emission. Our research provides scientific support for breaking the "technological energy paradox" in the field of energy economy while providing empirical evidence of "blockchain carbon reduction" for technologies such as blockchain BaaS alliance, cross-operator network spectrum, and shared base stations that will be applied on a large scale in the Industry 5.0 Era.