The most important synthetic methods including the Wurtz reaction, the activated alkali metal mediated reductive coupling, the electrochemical polymerization of dichlorosilanes using sacrificial anodes, the anionic ring-opening polymerization of tetrasilacyclobutanes and of masked disilenes, and the transition metal (Ti, Zr, Hf) catalyzed dehydrogenative coupling of hydrosilanes are briefly overviewed. A short discussion of the thermal and electronic properties of polysilanes allows for anticipating respectively their excellent processability and their technological applications. Among the latter, the most important ones appear to be microlithography for electronics, manufacture of light-emitting diodes (LEB) for various display devices, and fabrication of high tensile strength silicon carbide fibers, as well as heat resistant machineable objects. Other promising potential applications in optoelectronics are based on the interesting nonlinear optical (NLO) and photoconductive properties of suitably substituted polysilanes