Relationships have been obtained between intermonomer torsional angle and NMR chemical shifts ((1)H and (13)C) for isolated chains of two of the most important poly(9,9-dialkylfluorenes), poly[9,9-bis(2-ethylhexyl)fluorene-2,7-diyl] (PF2/6) and the copolymer poly(9,9-dioctylfluorene-co-[2,1,3]benzothiadiazole-4,7-diyl) (F8BT), using DFT calculations. The correlations provide a model for NMR spectral data interpretation and the basis for analysis of conformational changes in poly(9,9-dialkylfluorene-2,7-diyl)s. The correlations obtained for PF2/6 indicate that the (13)C chemical shifts of the aromatic carbons close to the intermonomer connection (C1, C2, and C3) have minimum values at planar conformations (0 degrees and 180 degrees ) and maximum values at 90 degrees conformations. In contrast, the (1)H chemical shifts of the corresponding aromatic ortho protons (Ha and Hb) are greatest for planar conformations, and the minimum values are seen for 90 degrees conformations. For the F8BT copolymer, similar relationships are observed for the (1)H (Ha, Hb, and Hc) aromatic shifts. Considering the aromatic carbons of F8BT, the behavior of C2, C4, C5, and C6 is similar to that found for the PF2/6 carbons. However, C1 and C3 of the fluorene moiety behave differently with varying torsion angle. These are in close proximity to the fluorene-benzothiadiazole linkage and are markedly affected by interactions with the thiadiazole unit such that delta(C1) is a maximum for 180 degrees and a minimum for 0 degrees , whereas delta(C3) is a maximum for 0 degrees and minimum for 180 degrees. We have studied the (1)H and (13)C spectra of the two polymers at temperatures between -50 degrees C and +65 degrees C. The observed changes to higher or lower frequency in the aromatic resonances were analyzed using these theoretical relationships. Fluorescence studies on PF2/6 in chloroform solution suggest there are no significant interchain interactions under these conditions. This is supported by variable-temperature NMR results. Polymer-solvent and polymer intramolecular interactions were found to be present and influence all of the alkylic and one of the aromatic (1)H resonances (Hb). The detailed attribution of the (1)H and (13)C NMR spectra of the two polymers was made prior to the establishment of the relationships between torsion angle and NMR chemical shifts. This was carried out through DFT calculation of the (1)H and (13)C shielding constants of the monomers, coupled with distortionless enhancement by polarization transfer and heteronuclear correlation NMR spectra. Several DFT levels of calculation were tested for both optimization of structures and shielding constants calculation. The B3LYP/6-31G(d,p) method was found to perform well in both cases.