The two-volume set LNCS 16063-16064 constitutes the proceedings of 20th European Conference on Technology Enhanced Learning, EC-TEL 2025, which took place in Newcastle upon Tyne and Durham, UK, September 2025.The total of 43 full papers, including 37 research papers, 4 blue-sky and 2 industry papers, as well as 16 demos and 32 posters papers presented in EC-TEL 2025 proceedings was carefully reviewed and selected from 195 submissions. They focus on all aspects of dynamic interdisciplinary field, bridging pedagogy, educational psychology, and digital technology.