For the first time, the room temperature synthesis of new Eu²⁺ doped hybrid materials together with their absorption and emission properties are reported. These hybrids containing Eu²⁺ and a small amount of Eu³⁺ are obtained through the hydrolysis and condensation of diethoxymethylsilane, methyltriethoxysilane and zirconium tetrapropoxide precursors in the presence of europium trichloride. These Eu²⁺ doped materials exhibit a strong host dependent Eu²⁺ luminescence, the intensity of which does not change upon air storage, confirming that Eu²⁺ ions are efficiently trapped inside these hybrid matrices.