Polysiloxanes have been found to be the most important and commercial family of synthetic inorganic polymers. The unique structure of the siloxane bond provides them with unusual features such as a high bond angle, nearly inexistent torsional barrier and a semi-ionic character due to the difference of electronegativities between the silicon and oxygen atoms. Also, silicon-based polymers have been used for the delivery of pharmaceutical and diagnostic compounds involving the use of nanoparticles with different shapes and sizes, as well as hydrogels, including those based on silicon compounds. Hydrogels based on silicon polyolates are rather promising. Some of them exhibit pronounced anti-inflammatory, regenerating, and protective activity, readily penetrate the organism and facilitate drug penetration into the tissues. Due to these properties, polysiloxanes have encountered a big opportunity as an important material in the area of biomedical engineering; the big influence they have in the area of prosthetic dentistry, tissue engineering, cell growth, wounded skin treatments is noteworthy. For the reasons briefly described above, we consider the fact of doing a review about how the polysiloxanes have been used over the years as polymeric matrices that are used in several applications in the field of biomedical engineering.