All-cis-tetrasiloxycyclotetrasiloxanes (Janus ring siloxanes) were facilely prepared from all-cis-cyclotetrasiloxanetetraol or sodium cyclotetrasiloxane silanolates. Moreover, we demonstrated the synthesis of extended Janus rings, [RSi(OR’)O]₄, containing various functional groups, via the Piers–Rubinsztajn reaction using a Janus ring siloxane as a precursor. Remarkably, we discovered the formation of an unexpected all-cis tricyclic laddersiloxane as a by-product. These synthesized compounds can be potential monomers of well-defined cage silsesquioxanes, Janus-type nanomaterials, and porous materials.