Si-based thermoelectric materials have attracted attention in recent decades with their advantages of low toxicity, low production costs, and high stability. Here, we report recent achievements on the synthesis and characterization of Si-based thermoelectric materials. In the first part, we show that bulk Si synthesized through a natural nanostructuring method exhibits an exceptionally high thermoelectric figure of merit zT value of 0.6 at 1050 K. In the second part, we show the synthesis and characterization of nanocomposites of Si and metal silicides including CrSi2, CoSi2, TiSi2, and VSi2. These are synthesized by the rapid-solidification melt-spinning (MS) technique. Through MS, we confirm that silicide precipitates are dispersed homogenously in the Si matrix with desired nanoscale sizes. In the final part, we show a promising new metal silicide of YbSi2 for thermoelectrics, which exhibits an exceptionally high power factor at room temperature.