Herein, we describe the synthesis and characterization of polymers formed by the Diels-Alder (DA) reaction between various difurans and divinylsulfone, and evaluate their dielectric properties. These syntheses were planned with computational support a priori in the form of HOMO/LUMO calculations for the dienes and dienophiles, with the calculated Delta E for the DA reactions ranging between 9.33 and 9.42 eV. We describe the structure-property relationship observed when changing an atom in the linking unit between two furan rings (-CH2-, -O-, -S-, -NH-) with respect to the dielectric constant and loss tangent. Dielectric constants for the polymers range between 4.96 and 5.98, with dielectric loss tangents ranging from 0.4 to 0.9% at 1 kHz and room temperature. Bandgaps of the polymers are elucidated with UV/Visible spectroscopy, and range from 2.15 to 2.61 eV. The retro DA onset is determined using three analytical methods: thermogravimetric analysis, dynamic scanning calorimetry, and gas chromatography/mass spectrometry polymer desorption spectroscopy, and is determined to be over 125 degrees C in all cases. (C) 2014 Elsevier Ltd. All rights reserved.