We performed Computational Fluid Dynamics (CFD) modeling, and simulated a people evacuation process from a tunnel in the event of a fire, for evaluating the potentialities of using, as a temporary safety measure, an emergency vehicle equipped with a micronized water system for contrasting the fire growth phase. The structure investigated is a one-way road tunnel with only natural ventilation, and with a length less than 1000 m. The tunnel is assumed at present to be affected by refurbishment works for making it comply with the minimum safety requirements of the European Directive 2004/54/EC. In particular, it is considered that it has not yet been provided with hydrants, and with the sidewalks and the emergency exit which are still under construction. This means that users are forced to use the road carriageway for escaping from the tunnel if a fire occurs. The CFD findings have shown that the use of the micronized water system might lead to a significant improvement in the environmental conditions along the escape route since the tenability limits of temperature, radiant heat flux, CO and CO2 concentration were found to be better satisfied. Additionally, the visibility distance was shown to increase, even though it was found to be higher than the acceptable threshold value only in a few cases. However, the quantitative risk analysis based on a probabilistic approach, which was combined with a method currently used in Europe for assessing the risk due to the transit of only dangerous goods, shows that the final cumulative F-N curves related to the micronized water system always lie below those without the mentioned system, and in addition, they are always contained within the limits of the ALARP region. It is to be stressed that our paper might represent a reference in showing the effectiveness of the micronized water system as a temporary safety measure. However, it is desirable that the Tunnel Management Agencies accelerate the refurbishment works for making road tunnels definitively safer for users in a short period of time.