Modern societies and industrial sectors are serviced through storage and distribution centres (SDCs) such as supermarkets, malls, warehouses, etc. Large quantities of supplies are stocked here, e.g., food grains, clothes, shoes, pharmaceuticals, electronics, plastics, edible oils, electrical wires/equipment, petroleum products, painting materials, etc. Fires due to the burning of these materials are categorized into six classes, viz., Class A, Class B, Class C, Class D, Class K, and Class F. A fire is extinguished better when the right type of fire retardant is used. A thumb rule on firefighting also says, “never fight a fire if you do not know what is burning”. In this paper, we have proposed an Intelligent Decision Support System (ID2S4FH) to generate a real-time ‘fire-map’ of such SDCs during a fire hazard. We have interfaced six tin-oxide-based gas sensor elements, a temperature and humidity sensor, and a particulate matter (PM) sensor with microcontrollers to capture the real-time signature patterns of the ambient air. We burned sixteen different types of materials belonging to six classes of fire and created a dataset consisting of 2400 samples. The sensor array responses were then pre-processed and analysed using various classifiers trained in different analysis space domains. Among the classifiers, four classifiers achieved ‘all correct’ identification of the fire classes of 80 unknown test samples, and the lowest mean squared error (MSE) achieved was 2.81 × 10−3. During a fire hazard, our proposed ID2S4FH can generate real-time fire maps of SDCs and help firefighters to extinguish the fire using the appropriate fire retardant.