Reactions of SiCl4 with R2PO(OH) (R=Me, Cl) yield compounds with six‐fold coordinated silicon atoms. Whereas R=Me afforded the hexacoordinated tetra‐cationic silicon complex [Si(Me2PO(OH))6]4+ with chloride counter‐ions, R=Cl caused release of HCl with formation of a cyclic dimeric silicon complex [Si(Cl2PO(OH))(Cl2PO2)3(μ‐Cl2PO2)]2 with bridging bidentate dichlorophosphates.