Silicene, a silicon analogue of graphene, has attracted increasing attention during the past few years. As early as in 1994, the possibility of stage corrugation in the Si analogs of graphite had already been theoretically explored. But there were very few studies on silicene until 2009, when silicene with a low buckled structure was confirmed to be dynamically stable by ab initio calculations. In spite of the low buckled geometry, silicene shares most of the outstanding electronic properties of planar graphene (e.g., the “Dirac cone”, high Fermi velocity and carrier mobility). Compared with graphene, silicene has several prominent advantages: (1) a much stronger spin–orbit coupling, which may lead to a realization of quantum spin Hall effect in the experimentally accessible temperature, (2) a better tunability of the band gap, which is necessary for an effective field effect transistor (FET) operating at room temperature, (3) an easier valley polarization and more suitability for valleytronics study. From 2012, monolayer silicene sheets of different superstructures were successfully synthesized on various substrates, including Ag(1 1 1), Ir(1 1 1), ZrB2(0 0 0 1), ZrC(1 1 1) and MoS2 surfaces. Multilayer silicene sheets have also been grown on Ag(1 1 1) surface. The experimental successes have stimulated many efforts to explore the intrinsic properties as well as potential device applications of silicene, including quantum spin Hall effect, quantum anomalous Hall effect, quantum valley Hall effect, superconductivity, band engineering, magnetism, thermoelectric effect, gas sensor, tunneling FET, spin filter, and spin FET, etc. Recently, a silicene FET has been fabricated, which shows the expected ambipolar Dirac charge transport and paves the way towards silicene-based nanoelectronics. This comprehensive review covers all the important theoretical and experimental advances on silicene to date, from the basic theory of intrinsic properties, experimental synthesis and characterization, modulation of physical properties by modifications, and finally to device explorations.