To enhance the fire suppression performance of Class A foam, this study identifies sodium dodecyl sulfate (SDS) as the primary foaming agent and develops a high-efficiency foam system comprising primary and auxiliary foaming agents, wetting agents, and foam stabilizers. It interprets these macroscopic findings at the molecular level through molecular dynamics simulations. Sixteen formulations were designed using orthogonal experiments and evaluated in terms of surface tension, viscosity, wetting performance, and foam expansion ratio. The results demonstrated that the formulated systems exhibited superior foaming characteristics compared to conventional aqueous film-forming foam (AFFF), while other physicochemical properties were inferior. Two high-performing foam systems were further investigated using molecular dynamics simulations. Analysis of the spatial concentration distributions, diffusion coefficients, and the hydrogen-bonding networks of water molecules revealed 14.3% and 14.2% increases in the peak values of the radial distribution function (RDF) for the two systems modified with auxiliary foaming agents, respectively. The auxiliary foaming agents exhibited synergistic effects with SDS, enhancing its water activation capability. The incorporation of wetting agents reduced the water diffusion coefficients by 4.7% and 21.9%, indicating that sodium bis(2-ethylhexyl) succinate sulphonate (T) interferes less with the primary foaming agent than alcohol ethoxylate (AEO). The selected formulations also demonstrated 4.4% and 3.5% reductions in water hydrogen bonding compared to SDS-only solutions, indicating decreased molecular cohesion and improved water activation. By integrating physicochemical evaluation with molecular simulation, the optimized formulation was determined to be SDS (primary foaming agent), sodium fatty alcohol ether sulfate (auxiliary foaming agent), alcohol ethoxylate (wetting agent), lauryl hydroxysultaine (foam stabilizer), and ethylene glycol butyl ether (cosolvent).