The underground coal gasification (UCG) represents an effective coal mining technology, where coal is transformed into syngas underground. Extracted syngas is cleaned and processed for energy production. Various gasification agents can be injected into an underground georeactor, e.g., air, technical oxygen, or water steam, to ensure necessary temperature and produce syngas with the highest possible calorific value. This paper presents an experimental study where dynamic optimization of operating variables maximizes syngas calorific value during gasification. Several experiments performed on an ex situ reactor show that the optimization algorithm increased syngas calorific value. Three operation variables, i.e., airflow, oxygen flow, and syngas exhaust, were continually optimized by an algorithm of gradient method. By optimizing the manipulation variables, the calorific value of the syngas was increased by 5 MJ/m3, both in gasification with air and additional oxygen. Furthermore, a higher average calorific value of 4.8−5.1 MJ/m3 was achieved using supplementary oxygen. The paper describes the proposed ex situ reactor, the mathematical background of the optimization task, and results obtained during optimal control of coal gasification.