According to the principles and the chemistries of the thermally-stable, conductive, or optical materials based on polymers, the author designed and synthesized a new series of bioprobes and biocompatible materials using cubic silsesquioxanes, nanoparticles, dendrimers, and network polymers as scaffolds. Herein, the recent works concerning these functional bio-related materials are described. In the former parts, the improvements of the sensitivity of the MRI contrast agents are presented. Furthermore, the developments of various kinds of the NMR probes for monitoring the biomolecules and biological reactions are explained. In the latter parts, the encapsulation abilities of the novel synthetic dendrimers and network polymers are illustrated. Finally, the photon upconversion system in aqueous solutions is reported for extending the applicability of photomedical treatments at the deep spots inside vital bodies.