A tungsten hydride complex, [WH2(η2-OOCCH3)(Ph2PCH2CH2PPh2)2][BPh4], was dispersed in a hybrid matrix synthesized by a sol–gel process. The host matrix of the so-called ureasil is a network of silica to which oligopolyoxyethylene chains [POE, (OCH2CH2)n] are grafted by means of urea cross-links. The free complex and sol–gel materials were characterized by thermal analysis (DSC) and spectroscopic methods (FT-IR and UV/Vis). The data gathered indicate that the tungsten(IV) complex is immobilized in the host matrix, and it exhibits structural properties different from those of the free form. These differences could arise either from distortions caused by steric effects imposed by the structure of hybrid matrix or by interactions with the matrix.