Transition metal silicides have attracted great attention due to their potential applications in microelectronics, ceramics, and the aerospace industry. In this study, experimental and theoretical investigations of tungsten based silicides were performed. Tungsten disilicide (WSi₂) was synthesized by simple thermal treatment at 1350 °C for 4 h in an argon atmosphere. These optimal synthesis conditions were obtained by variation of temperatures and times of heating, and the structure of the final synthesized compound was determined by XRPD analysis. In addition, new modifications for WSi₂ were proposed and investigated using first‐principles calculations within density‐functional theory (DFT). Both LDA and PBE calculations show excellent agreement with experimental observations and previous calculations for the existing modifications, where available.