Reaction of UO2I2(THF)3 with 1 molar equivalent of KC5R5 (R = H, Me) in pyridine led to the uranyl(V) compound {[UO2(Py)5][KI2(Py)2]}(infinity), which is an infinite 1D polymer in its crystalline form; the UO2X(THF)n (X = I, OSO2CF3) complexes were obtained by reduction of their U(VI) parents with TlC5H5 or KC5R5 in THF.