Silicene is a two-dimensional(2D) material, which is composed of a single layer of silicon atoms with sp2–sp3mixed hybridization. The sp2–sp3mixed hybridization renders silicene excellent reactive ability, facilitating the chemical modification of silicene. It has been demonstrated that chemical modification effectively enables the tuning of the properties of silicene. We now review all kinds of chemical modification methods for silicene, including hydrogenation, halogenation,organic surface modification, oxidation, doping and formation of 2D hybrids. The effects of these chemical modification methods on the geometrical, electronic, optical, and magnetic properties of silicene are discussed. The potential applications of chemically modified silicene in a variety of fields such as electronics, optoelectronics, and magnetoelectronics are introduced. We finally envision future work on the chemical modification of silicene for further advancing the development of silicene. Silicone is a two-dimensional (2D) material, which is composed of a single layer of silicon atoms with sp2-sp3mixed hybridization. It has been demonstrated that chemical modification effectively enabling the tuning of the properties of silicene. We now review all kinds of chemical modification methods for silicene, including hydrogenation, halogenation, organic surface modification, oxidation, doping and formation of 2D hybrids. The effects of these chemical modification methods on the geometrical, electronic, optical, and magnetic properties of silicene are discussed. The potential applications of chemically modified silicene in a variety of fields such as electronics, optoelectronics, and magnetoelectronics are introduced. We finally envision future work on the chemical modification of silicene for further advancing the development of silicene.