By use of highly oriented films, the polarization dependence of the C 1s and F 1s near-edge absorption spectra of poly(tetrafluoroethylene) has been measured. At le ast at the carbon K edge, good agreement is obtained with the predicted behavior based on a consideration of the one-dimensional band structure and the effect of symmetry breaking. The findings are also relevant for the assignment of the resonances in long chain alkanes, a subject which has recently been somewhat controversial.