The growth mechanism of amorphous carbon film by the liquid deposition process is still unclear. In this study, the influence of applied voltages on the surface morphology and microstructure of amorphous carbon films was investigated as well as the bonding probability at the film/substrate interface, and a new mechanism of film growth was proposed from the electrochemistry and non-equilibrium thermodynamics viewpoints. The results showed that growth of amorphous carbon film involved the island groove morphology; more graphitic carbons are present within the film as the applied voltage increased. A coupling model of the growth mechanism including the ionization-absorption-dehydrogenation process and the chemical volume polymerization is highlighted. Copyright (c) 2016 John Wiley & Sons, Ltd.