Exploration of new ways for the direct preparation of cross-linked structures is a significant problem in terms of materials for biomedical applications, lithium batteries electrolytes, toughening of thermosets (epoxy, benzoxazine, etc.) with interpenetrating polymer network, etc. The possibility to utilize hydrosilylation and Piers–Rubinsztajn reactions to obtain cross-linked model phosphazene compounds containing eugenoxy and guaiacoxy groups has been studied. It was shown that Piers–Rubinsztajn reaction cannot be used to prepare phosphazene-based tailored polymer matrix due to the catalyst deactivation by nitrogen atoms of main chain units. Utilizing the hydrosilylation reaction, a series of cross-linked materials were obtained, and their properties were studied by NMR spectroscopy, FTIR, DSC, and TGA. Rheological characterizations of the prepared tailored matrices were conducted. This work showed a perspective of using eugenoxy functional groups for the preparation of three-dimensional hybrid phosphazene/siloxane-based materials for various applications.