Thiol–ene click reaction was employed to synthesize a flexible hydrophilic cellulose sponge. The reactive vinyl group was introduced by silanization treatment with vinyl-trimethoxysilicane (VTMO), and the resulting silylated cellulose sponge (SCS) can be subsequently functionalized with various thiol-containing compounds such as 3-mercaptopropionic acid, via temperature induced thiol–ene reactions. The hydrophilic cellulose sponge thus prepared displayed an excellent mechanical strength of 70 KPa at 80% compression strain. The prepared sponge features hydrophilic and underwater oleophobic properties and was used in gravity-driven removal of oil from oil-in-water emulsions and oil/water mixtures with a high separation efficiency. The separation efficiency remained 100% after 10 cycles for an oil/water mixture and 95% after 6 cycles for an oil-in-water emulsion.