Cyclic silanol derivatives (CSDs), possessing siloxane rings consisting of T-unit silicon and oxygen atoms, are considered efficient precursors for the preparation of versatile well-defined building blocks of hybrid materials such as cyclic, cage- or ladder-type SQs. This review provides an outline of the main synthetic routes to numerous stereoregular CSDs with different sizes of siloxane rings since the first example of CSDs reported by Brown et al. in 1965. The typical reaction conditions and chemical shifts of 29Si NMR of all mentioned CSDs in this review are summarized in tables and schemes to recapitulate the state of the art. The synthesis of all-cis-cyclotetrasiloxanes (T4), the most investigated CSDs, and their functionalization by different organic reactions to access various all-cis-T4 with functional groups are methodically presented. Moreover, the potential of CSDs in multiple application fields is discussed to show the possible research directions of this family of compounds in the future.