In this study, the first route to synthesize a compound with the guarinoite structure (Zn,Co,Ni) 6 (SO 4 ) (OH,Cl) 10 Γ 5H 2 O is reported. Zn/Ni guarinoite is obtained from the reaction of NiSO 4 Γ 7H 2 O with solid ZnO in aqueous solution. The resulting green Zn/Ni guarinoite ((Zn 3.52 Ni 1.63 ) (SO 4 ) 1.33 (OH 7.64 ) Γ 4.67H 2 O) was characterized by X-ray diffraction, infrared spectrometry, UV-Visible spectrometry and thermal analysis. It is shown that its structure is similar to the one described for the layered Zn sulfate hydroxide hydrate, i.e. brucite layers with 1 4 empty octahedra presenting tetrahedrally coordinated divalent atoms above and below the empty octahedra. Ni atoms are located in the octahedra and zinc atoms in tetrahedra and octahedra. In this structure the exchangeable anions are located at the apex of tetrahedra. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations show that the Zn/Ni guarinoite is composed of aggregates of hexagonal plates of several hundreds of nanometers. Due to its interest for industrial or environmental applications, the exchange of sulfate groups by carbonates has been investigated. Results show a limited exchange and a higher affinity of the Zn/Ni guarinoite for sulfates compared to carbonates.