Density functional theory (DFT) and variational density functional perturbation theory (DFPT) simulations of amorphous poly-CO structures were performed to understand the stability of the polymerized structure at low pressures and to study the mechanism of destruction of the extended network at low pressures. Charge population analyses accompanied the search of the “weakest link” in the covalently bonded network. IR and Raman spectra of amorphous p-CO, calculated at 15 and 5.02 GPa, show significant contributions of CO molecules, carbonyl groups fragments decorating chains, and lactones of amorphous p-CO structures. DFT simulations of formation of amorphous polymeric structures were also done with the addition (as a result of replacement of CO molecules) of N or He atoms to the crystalline delta phase of CO. For the CO-N mixtures, the concentration of N was varied in the range from 6.25 % to 50% with different distribution patterns of N atoms in the unit cell. For all studied CO-N concentrations, isotropic compression led to CO polymerization beginning at a pressure of 11 GPa; the N was incorporated in the random network in low concentration. In CO-He mixtures He atoms appear to facilitate complete formation of the random structure which is almost completely polymerized at a pressure of 18 GPa. He atoms also help stabilize the structure at low pressures.