Three different X-ray analysis techniques were used to investigate the chain defect content present in the crystalline regions of poly(vinyl fluoride). The techniques used were a fiber pattern analysis, a powder pattern analysis, and a meridional intensity analysis. The fiber pattern analysis proved unable to determine either the tacticity or regic defect content in PVF. However, it was found that the refinement favored a statistical packing of the chains in the crystalline regions. This packing arrangement was supported by the powder pattern analysis and molecular modeling calculations. The meridional intensity analysis proved to be sensitive to the regic defect content of the sample. The results of this analysis correlated well with previous DSC work.