Population and development megatrends will drive growth in cement production, which is already one of the most challenging-to-mitigate sources of CO₂ emissions. However, availabilities of conventional secondary cementitious materials (CMs) like fly ash are declining. Here, we present detailed generation rates of secondary CMs worldwide between 2002 and 2018, showing the potential for 3.5 Gt to be generated in 2018. Maximal substitution of Portland cement clinker with these materials could have avoided up to 1.3 Gt CO₂-eq. emissions (~44% of cement production and ~2.8% of anthropogenic CO₂-eq. emissions) in 2018. We also show that nearly all of the highest cement producing nations can locally generate and use secondary CMs to substitute up to 50% domestic Portland cement clinker, with many countries able to potentially substitute 100% Portland cement clinker. Our results highlight the importance of pursuing regionally optimized CM mix designs and systemic approaches to decarbonizing the global CMs cycle.