Poly(phenylene ethynylene) (PPE) and a series of PPE derivatives were studied using density functional theory tight binding to generate molecular dynamics simulations in the gas phase. Dihedral angles between adjacent phenylene units were measured over time to generate a histogram of conjugation lengths, where the conjugation length was defined by planarity. The average effective conjugation lengths for these polymers were extracted from this data. Notably, it was found that PPE with alkoxy substituents on the phenylene ring of each repeat unit is attributed to causing an increased average conjugation length relative to unsubstituted PPE from 4.7 to 6.4 repeat units. Comparatively, alkyl substituents caused a decrease in the conjugation length to 4.5 repeat units. The methods developed here were extended to a wider series of PPE derivatives, where a direct link was found between polymer planarity and the electron-donating/-withdrawing ability of substituents. These results indicate that the solvating side chains frequently employed in conjugated polymers have an innate effect on the rigidity of the polymer backbone.