The incorporation of aluminum in magnesium silicate hydrate (M-S-H) phases was investigated. Magnesium (alumino) silicate hydrate (M-(A-)S-H) with Mg/Si ratios equal to 1.1 or 1.7 and Al/Si ranging from 0 to 0.2 were synthetized in batch experiments and equilibrated at 20, 50 and 70 °C. pH values between 9 and 10.5 were observed and aluminum up to Al/Si ~0.15–0.18 was incorporated in M-(A-)S-H. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray pair distribution function (PDF) analysis, transmission electron microscopy (TEM), ²⁹Si and ²⁷Al MAS NMR data showed that the M-(A-)S-H phases formed were similar to M-S-H with limited coherent size and a comparable polymerization degree of the tetrahedral silicates. Aluminum was incorporated in both tetrahedral and octahedral sites of M-S-H, while no aluminum was present as exchangeable cation on the surface sites.