The addition of 10 wt% aluminum hydroxide to two crude kaolinitic clays, a commercial and a natural freshly mined one, has enhanced their pozzolanic activity, more substantially in the natural sample containing gibbsite. The obtained blends were used as replacement of 20 wt% of Portland cement in the formulations of pastes and mortars which exhibited significant decrease of setting time and increase of compressive strength from early age to 28 days. Also, SEM/EDX analyses showed very heterogeneous structures with hydrated phases identified from XRD. Specific interpretation of the role played by aluminum hydroxide revealed its aptitude to promote the formation of metastable hydrated phases (CAH10/C2AH8) at early age, which temporally inhibited the hydration of cement. This progressive transformation led to the formation of more stable hydrated phases such as C-A-S-H which favored the increase of mechanical strength of the specimens. The sequence of transformation reactions is fully obtained with limited aluminum hydroxide content in clays. Either added as synthetic or naturally occurring in clays, aluminum hydroxide has close role in the strengthening process of cement. Hence, kaolinitic clays that naturally contain gibbsite are suggested as suitable supplementary cementitious material for partial replacement of cement.