The implementation of photoinduced linkage isomerism in molecular-based optical materials represents a promising approach for the synthesis of high-contrast, high-resolution photosensitive materials that are necessary for high-density (holographic) data storage and/or real-three-dimensional (holographic) displays. The unsolved task of embedding a photofunctional coordination complex into a matrix like polymer polydimethylsiloxane (PDMS) with photoinduced isomerism of a SO-bond in the sulfoxide compound [Ru(bpy)₂OSO]PF₆ is addressed. This approach allows to preserve the spectral properties within the solid dielectric environment, with an impact of PDMS on population and relaxation dynamics. All data are discussed in the framework of photofunctionality, storage, and display applications.