Water and foam have different fire-extinguishing mechanisms. Traditional foam and compressed air foam (CAF) have different bubble structures. These differences result in different thermal characteristics, which affect the extinguishing abilities during a fire. In this study, the differences in the thermal characteristics of three different extinguishing agents (water, traditional foam, and CAF) were investigated by suppressing a compartment fire. With an ignition source in the compartment (6 m × 3 m × 3 m), the agent was preferentially applied to the outside wall of the compartment. The effects of internal cooling and burnback resistance generated from the outer wall were evaluated. The performance of each agent in shielding firefighters from radiant heat while suppressing the fire inside the compartment was evaluated. When the outside wall of the compartment was covered with each of the agents, all agents were found to reduce the room temperature. When CAF was applied, the delay time until temperature re-rise was approximately 1.76–4.5 times longer than that when water was used. In addition, foaming agents exhibited a higher heat-shielding effect than water during the initial suppression. Thus, considering the thermal characteristics of these agents, fire suppression can be more effective if foam agents are used.