The reactions of tellurium tetrahalides and triphenylphosphine in tetrahydrofuran have been carried out under ambient conditions and afford {(Ph3PO)(2)H}(2)[Te2X10] [X = Cl (1), Br (2)] and {(Ph3PO)(3)(OH3})(2)[Tel(6)] (4). The X-ray structures of 1 and 2 show that they are isostructural and contain discrete [Te2X10](2-) anions exhibiting octahedral coordination around both tellurium atoms with one shared edge and {Ph3POH...OPPh3}(+) cations that show strong hydrogen bonds (the O...O distances are 2.399 and 2.404 Angstrom for 1 and 2, respectively). The compound 4 is built up with discrete octahedral hexaiodotellurate anions and {(Ph3PO)(3)(OH3)}(+) cations. The reaction of TeBr4 and PPh3 also results in the formation of formally zwitterionic Ph3PO(CH2)(4)TeBr4 (3). This reaction involves an unprecedented THF ring opening in which the oxygen atom becomes bonded to the phosphorus atom of triphenylphosphine and the carbon atom at the other end of the five-atomic chain becomes bonded to the tellurium atom of TeBr4. The ring opening of the solvent THF is also taking place in the reaction involving tellurium tetraiodide, as indicated by the formation Of C(4)H(8)Tel(2) (5). The reaction may initially lead to Ph(3)Pl(2) that reacts with THF yielding Ph3PO and ICH2(CH2)(2)-CH2I. The latter species reacts with elemental tellurium producing 5. Depending on the conditions upon crystallization, two polymorphs Of C(4)H(8)Tel(2) (5a and 5b) are observed. While the molecular structures of the two forms are virtually identical, their packing and intermolecular contacts are different. Two further minor products (6a and 6b) were isolated in the reaction of Tel(4) and PPh3: Both are formally 1:1 adducts of 5 and Tel(4), but they differ considerably in their structures. 6a can be formulated as {C(4)H(8)Tel(+)}(2)[Te2I102-] and 6b as {C(4)H(8)Tel(+)}(2)(Tel(3+))(2)(I-)(4). The latter compound exhibits framework similar to that of the tetramers in gamma- and delta-Tel(4).