The reaction of bis(2-furyl) ditelluride Fu 2 Te 2 (1) with iodine in diethyl ether under ambient conditions expectedly yields FuTeI (2). The in situ reaction of 2 with triphenylphosphine affords Ph 3 PTe(Fu)I (3), which was characterized in the solid state by single crystal X-ray crystallography. The crystal structure of 3 shows linear P–Te–I backbone and T-shaped coordination around the tellurium atom. In the solid lattice, 3 exists as discrete molecules, which are lined together by a H⋯I hydrogen bonding network. There is no evidence of the secondary bonding Te⋯I or I⋯I interactions, which are typical for many tellurium–iodine compounds. When this two-step reaction of Fu 2 Te 2 with I 2 and PPh 3 is carried out in tetrahydrofuran, a mixture of products is obtained. The main products, which were identified by single-crystal X-ray crystallography, are {Ph 3 P(C 4 H 5 O 2 )} 2 [TeI 4 ] (4), {Ph 3 P(CH 2 ) 4 PPh 3 }[TeI 4 ]·2CH 2 Cl 2 (5·2CH 2 Cl 2 ), Fu 2 Te (6), (CH 2 ) 4 TeI 2 (7), Ph 3 PO, and elemental tellurium. The formation of the products has been discussed in terms of THF ring opening, abstraction of tellurium by PPh 3 , and the conversion of the furyl ring in FuTeI into a lactone ring due to the presence of atmospheric moisture.