This paper describes an alternative process for chloroform decomposition via nonthermal plasma polymerization at atmospheric pressure and investigates the effect of methane and hydrogen addition on the process. The effect of both additives was assessed separately, where experiments were conducted in a double dielectric barrier discharge reactor under nonoxidative conditions. The most profound impact of the additives was a significant increase in the yield of non-cross-linked polymer produced compared to that in their absence. The addition of methane resulted in a 120% increase in polymer yield, while in hydrogen the increase was 31%. Critical parameters such as effect of the methane and hydrogen concentration on the conversion of chloroform at various applied voltages, the product distribution, mass balance, and polymer characterization are elucidated in this paper. Single pass conversions of 61% and 68% (with corresponding mass balances of 98% and 95%, respectively) were achieved for CHCl3 + CH4 and CHCl3 + H-2 feed scenarios, respectively. Furthermore, a polymerization mechanism which explains the formation of major chain structures as well as structural defects in the polymer is expounded upon in the paper.