The reaction network of benzene as a byproduct in the production of vinyl acetate from the acetylene process was further improved by density functional theory (DFT). The mechanism of the byproduct acetaldehyde as a competitive reaction was also systematically studied by DFT. Kinetic Monte Carlo (KMC) was used to further study the main reaction and various side reactions in the process of producing vinyl acetate from acetylene. The effects of temperature, pressure, and molar ratio of acetylene/acetic acid on the reaction process were investigated. Under the process conditions of 453 K, low pressure, and low molar ratio of acetylene/acetic acid in the range of 2-2.6, the formation of byproduct benzene is inhibited.