A new approach for the thermal reduction of tin dioxide (SnO2) in the carbon/sodium sulfite (Na2SO3) system is demonstrated. The process of tin smelting was experimentally optimized by adjusting the smelting temperature and amounts of the chemical components used for the thermal reduction of SnO2. The numbers obtained are consistent with the thermodynamic characteristics of the system and molar fractions of reactants derived from the proposed mechanism of the SnO2 thermal reduction process. They reveal that the maximum yield of tin is obtained if masses of C, Na2SO3 and SnO2 are approximately in the ratio 1:2:3 and the temperature is set to 1050 °C. The key role in the suggested mechanism is the thermal decomposition of Na2SO3. It was deduced from the available experimental data that the produced sulfur dioxide undergoes carbothermic reduction to carbonyl sulfide—an intermediate product involved in the bulk reduction of SnO2. Replacing sodium sulfite with sodium sulfate, sodium sulfide and even elemental sulfur practically terminated the production of metallic tin. The kinetic analysis was focused on the determination of the reaction orders for the two crucial reactants involved in the smelting process.