Polynitroxides with varying numbers of nitroxide groups (one to four), derived from different aromatic core structures show intramolecular electron spin-spin coupling. The scope of this study is to establish an easy methodology for extracting structural, dynamical, and thermodynamical information from the EPR spectra of these polynitroxides which might find use as spin probes in complex systems, such as biological and host/guest systems, and as polarizing agents in dynamic nuclear polarization (DNP) applications. Density functional theory (DFT) calculations at the B3LYP/6-31G(d) level provided information on the structural details such as bond lengths and angles in the gas phase, which were compared with the single crystal X-ray diffraction data in the solid state. Polarizable continuum model (PCM) calculations were performed to account for solvent influences. The electron paramagnetic resonance (EPR) spectra of the polynitroxides: in chloroform were analyzed in detail to extract information such as the percentages of different conformers, hyperfine coupling constants a, and rotational correlation times tau(c). The temperature dependence on the line shape of the EPR spectra gave thermodynamic parameters Delta H and Delta S for the conformational transitions These parameters were found to depend on the number and relative positions of the nitroxide and other polar groups.