Trimethylsilylation of metal oxide surfaces (silica, titania…) is a common way to empower the handled supports with outstanding stability. This hydrophobisation prevailed in vital domains including chromatographic column, adsorption-based membranes and heterogeneous catalysis, where hydrolytic stability constituted a challenging issue. In spite of its benefits, trimethylsilylation of graphene oxide has been only sporadically investigated and this underlooked chemistry needs to be accurately addressed for further tailoring the surface properties of graphene materials. With this aim, we herein screened a set of commercially available trimethylsilyl reagents for end-cuping the surface of graphene oxide. Surprisingly, meticulous investigations show that these reagents behave primarily as nucleophiles and induce oxirane opening, with a diverging pattern depending on the functional group linked to trimethylsilyl fragments. Specifically: i) trimethylsilylchloride and trimethylsilyltriflate are not suitable because of the substantial side products formed under acidic conditions; ii) trimethylsilylimidazolium reacts rather through its imidazolium group with the simultaneous elimination of trimethylsilyl groups; iii) bis-silylated reagents like hexamethyldisilazane and N,O-bis-trimethylsilyl-trifluoroacetamide enable anchoring at least one functional arm while liberating the second trimethylsilyl moity. The introduced functionalities enhance the dispersion of the newly prepared graphenes in liquid medium, thereby broadening the library of solvents suitable for their handling and offering more possibilities for the ink processability. Regardless of the starting reagent, the resulting functionalisation do not compromise the anchoring ability of the graphene surface as illustrated by supporting InP/ZnS semiconductor nanocrystals. In the whole, these serendipitous findings challenge the conventional wisdom about the reactivity of trimethylsilyl reagents that was primarly associated to surface hydrophobisation, opening indeed new possibilities for graphene functionalisation and further use in materials science.