A better understanding of the chemistry of terphenyls production is required due to its contribution to the petrochemical industry and its usage in the production of useful raw materials. A benzene pyrolysis study was conducted with pure benzene, benzene with biphenyl and acetylene and benzene with CO2 mixed with N2 as diluent. This study aims to provide better insights into the effect of additives on terphenyls through pyrolyzing different fuels which were carried out in a jet-stirred reactor under atmospheric pressure, temperature range of 700-1250 K and residence time of 3s. The experimental data were measured by GC (gas chromatography) and plotted versus the temperature range provided four different kinetic models were simulated to compare with the experimental data of the reactants and products. Numerical analyses were conducted to gain a deep understanding of the main pathways that affect terphenyl isomers. A significant amount of soot was noticed at high temperatures (1200-1250 K) which was considered a soot area where the measurements may have affected. The addition of biphenyl and acetylene to benzene pyrolysis speeds the benzene consumption at high temperatures provided it showed a boost in m-terphenyl formation compared to pure benzene. In addition, acetylene addition increases the production of small hydrocarbons and the production of m-terphenyl was inhibited due to the change in the chemistry that acetylene follows. In the comparison of the experimental data with simulations, a good agreement was noticed for some compounds. Biphenyl addition is less sensitive toward H-abstraction reaction compared to pure benzene. Additionally, kinetic simulations of different residence times and pressures show an increase with increasing both factors and vice versa, based on the selected model. A shift in the speciation profiles was seen where the effect on reactants was noted at lower temperatures for higher residence time and pressure.