New compound Zn[(S,S)-iPr-pybox](Et)₂ (1) was fully characterized, including by X-ray diffraction structural studies. Its grafting onto partially dehydroxylated silica affords material 2, which bears well-defined chiral (SiO)Zn[(S,S)-iPr-pybox](Et) sites. Hybrid material 2 displays significantly better catalytic performances than 1 in enantioselective silylcyanation, thus demonstrating a beneficial grafting effect.