This volume gathers the latest advances, innovations and applications in the field of sustainable construction materials and structures, as presented by leading international researchers and engineers at the 75th RILEM Annual Week (75RW 2021), held in Merida, Mexico on August 29 - September 3, 2021. It covers topics such as supplementary cementitious materials, durability and Life Cycle assessment in urban and marine conditions, additive manufacturing of concrete in construction, structural performance and design, non-Portland cements and Alkali activated cementitious materials and eco-concrete, cultural heritage, non-destructive testing techniques, bituminous materials, and construction materials (polymers, timber, bamboo, recycling and masonry). The contributions, which were selected through a rigorous international peer-review process, share exciting ideas that will spur novel research directions and foster new multidisciplinary collaborations.