The structural build-up of cementitious materials is the subject of more and more attention since it conditions several processes such as formwork pressure and multi-layer casting. However, this phenomenon originating from flocculation and chemical changes is complex and its reversibility is not clearly elucidated. The aim of this paper is to examine the effect of temperature on the reversibility of structural build-up. The results show that irreversible structural build-up remains negligible despite a rise in temperature. It represents between 0.5–7.3% of the total structural build-up. The addition of SCMs allows for a decrease in this irreversible structural build-up. Therefore, a large part of the chemical contribution is expected to be reversible. The effect of temperature can be explained by the increase in the dissolution rate leading to an increase in flocculation and to the bridging effect induced by early hydrates. Finally, the results suggest that the interparticle distance could be the key parameter governing the irreversibility of structural build-up.