We present a new methodology that couples neutron diffraction experiments over a wide Q range with single chain modelling in order to explore, in a quantitative manner, the intrachain organization of non-crystalline polymers. The technique is based on the assignment of parameters describing the chemical, geometric and conformational characteristics of the polymeric chain, and on the variation of these parameters to minimize the difference between the predicted and experimental diffraction patterns. The method is successfully applied to the study of molten poly(tetrafluoroethylene) at two different temperatures, and provides unambiguous information on the configuration of the chain and its degree of flexibility. From analysis of the experimental data a model is derived with C-C and C-F bond lengths of 1.58 and 1.36 angstrom, respectively, a backbone valence angle of 110-degrees and a torsional angle distribution which is characterized by four isometric states, namely a split trans state at +/- 18-degrees, giving rise to a helical chain conformation, and two gauche states at +/- 112-degrees. The probability of trans conformers is 0.86 at T = 350-degrees-C, which decreases slightly to 0.84 at T = 400-degrees-C. Correspondingly, the chain segments are characterized by long all-trans sequences with random changes in sign, rather anisotropic in nature, which give rise to a rather stiff chain. We compare the results of this quantitative analysis of the experimental scattering data with the theoretical predictions of both force fields and molecular orbital conformation energy calculations.