Graphite oxide was silylated by various alkylchlorosilanes in the presence of butylamine and toluene, and new intercalation compounds were obtained. The silylating reagents with two or three chlorine atoms at silicon in them reacted with graphite oxide, while no reaction occurred when silylating reagents with only one chlorine atom was used. The silylating reagent mainly reacted with hydroxyl group of graphite oxide, forming Si–O bonding. The role of butylamine was not only exfoliating graphite oxide layer but also scavenging HCl molecule which caused the decomposition of silylated graphite oxide. The silicon content was almost constant ≈0.6 mol/graphite oxide for the samples silylated by alkyltrichlorosilane with shorter alkyl chain lengths. It increased with the increase of alkyl chain length and reached 1.7 mol/graphite oxide. The higher silicon content could be ascribed to further silylation on hydroxyl groups formed at silicon atoms of silylating reagent bonded to graphite oxide, bridging two silylating reagents.