Telomerization of tetrafluoroethene with ethylene glycol monomethyl ether in the presence of t-butyl peroxide at 115℃ to 130℃ was shown to yield three products, namely 1, b. p. 154℃; 2. b, p. 164℃ and 3, b. p. 177℃, with ethylene glycol dimethyl ether two series of products were obtained, namely, 4, b. p. 131℃; 9, b. p. 167℃ and 5, b. p. 147℃; 10, 179℃ respectively. These products were separated by fractional distillation. Their structures were established by chemical, transformations and inter-conversions, and confirmed by IR and NMR spectroscopy.