Homogeneous polymerizations of tetrafluoroethylene (TFE) were executed in supercritical fluoroform (scCHF 3 ), and the resulting poly(tetrafluoroethylene) (PTFE) was uniformly dispersed and twined fibers (ca. 100 nm in width and 10 µm in length). The number-average molecular weight and the conversion of PTFE can be controlled by pressures of scCHF 3 from M n ) 10 4 to 10 6 and 60-80%, respectively. Heterogeneous detergentfree or stabilizer-free emulsion polymerization could be performed in the narrow condition of the scCHF 3 /water (5:3 in v/v) system at 17 MPa of the pressure with the 20-40% conversion, and the uniform spherical submicron particles (ca. 200 nm) of PTFE were obtained, in comparison with twined fibers from the homogeneous polymerization.