Organic-inorganic hybrid materials find many applications in catalysis, nanotechnology, electronics, and many others. Grafting organic functionalities on inorganic supports is one of the most used methods for their preparation. Toluene is the solvent of choice for the grafting reaction, but it is fossil fuel-derived and not devoid of toxic effects. In this work, we explore the use of sustainable alternatives, i.e., (+)-α-pinene, (-)-β-pinene, dimethyl carbonate (DMC), (+)-limonene, and 2-methyl-tetrahydrofuran (MeTHF), as solvents for grafting. The grafting reaction between 3-aminopropyltriethoxysilane (APTS) and mesoporous ordered silica (MCM-41) was selected as a model for this study. A comparison of the rate of the grafting reaction in different solvents is reported. The resulting hybrid materials were analyzed by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA) and compared to the reference material prepared in toluene. MeTHF proved to be the best sustainable alternative to toluene for model grafting, providing a comparable product in a significantly shorter reaction time.