Polysiloxanes are a kind of polymers having Si-O main chains. Si-O bond is long, with partial double-bond and substantial ionic characters, and high bond dissociation energy. Furthermore, the value of the Si-O-Si angle is high. The features of Si-O bond make polysiloxanes have many excellent performances, such as high and low temperature resistance, radiation resistance, weathering resistance, electrical insulation, ozone resistance, water repellence, fire retardance, non-toxic, no corrosion, and physiological inertia. Polysiloxanes are important materials in several areas, for example, in aerospace, architecture, electronics, daily chemicals, and medicines. Besides, the raw materials for preparation of polysiloxanes are abundant. Expanding the application range of polysiloxanes can help human beings reduce the dependence on non-renewable resources. On the other hand, improving the performances of polysiloxanes can further expand the application range of polysiloxanes. And the performances of polymer materials mainly depend on their main chain structures. Consequently, the preparation of polysiloxanes having special topologies is a key point. In this paper, the research progress of synthesis, properties, and application of polysiloxanes with special topologies, including macrocyclic, closed multicyclic, hyperbranched, cage, semi-cage, double-decker-shaped, and ladder polysiloxanes, are introduced.