Abstract Benzonitrile (BZN) and carbon tetrachloride (CCl 4 ) are versatile solvents used as a precursor for the synthesis of many products. As multi‐usage molecules, these compounds may be involved in sustainable chemistry processes such as the cold plasma techniques for which the generated electrons are known to be responsible for reactions. Therefore, it is desirable to explore the interaction of low energy electrons with the co‐compounds in the gas phase. The production of chlorine and cyanine anions, initiated by the electron collision with CCl 4 and BZN, respectively, undergo nucleophilic substitution S N 2 reaction with the precursors molecules for the synthesis of chlorobenzene and tricholoacetonitrile. The mechanism of fragmentation of benzonitrile and the synthesis reactions are rationalized by DFT calculations. The yield of the cyanine anion produced from the ion reaction increases with the temperature of the admixture gas, probed in the 25–100 °C temperature range. The present work may contribute to a potential process for the production of chlorobenzene for instance via (cold) plasma techniques.