Quantum mechanical (semiempirical) and force field calculations of oligomers of recently reported polycarbyne network backbone polymers indicate that calculated bond lengths between adjacent carbon backbone atoms are elongated relative to the bond distance of a C-C single bond. Some degree of bond cleavage is theorized to occur between adjacent carbon atoms of the polymers’ network backbones, resulting in the formation of biradicals. This theory is supported experimentally by the polymers’ electronic absorption spectra, their degrees of polymerization, and their ESR spectra, which show a decreasing signal as the steric bulk between adjacent carbons is decreased.