Molecular modeling techniques were used to investigate the influence of chain defects in poly(vinyl fluoride) upon the crystallization energetics. The analysis considered the presence of tacticity and regic defects in poly(vinyl fluoride) upon the crystallization energetics. The analysis considered the presence of tacticity and regic defects in both syndiotactic and isotactic chains. Calculations were performed to determine the conformational, configurational, and constitutional energies for several different isolated chains and the packing energies for various chains contained in a crystalline region. From the modeling results, inferences were drawn regarding the crystallizability of chain sequences containing the above-mentioned defects. In general, it was found that a chain sequence which contains a defect does not incur a significant energy penalty when incorporated into a crystalline region. Of the defects considered, the isotactic unit produced the least energetically favorable, structure relative to any other chain defect.