An experimental study of the ignition and combustion processes of coal-water slurry (CWS) droplets based on coal enrichment waste in a high-temperature oxidizer at 650−850 °C with a syngas addition was carried out. The fuel slurry was a mixture of finely dispersed solid combustible particles (coal sludge, 10−100 µm in size) and water. The syngas was a product of biomass pyrolysis and two waste-derived fuels in a laboratory gasifier. Composition of the syngas was controlled by a precision analytical gas analyzer. The feasibility of co-firing CWS with syngas was experimentally established. Under such conditions, the CWS droplets ignition process was intensified by 15−40%, compared to fuel combustion without the addition of syngas to the combustion chamber. The greatest positive effect was achieved by adding the gas obtained during the biomass pyrolysis. The ignition delay times of CWS droplets are 5.2−12.5 s versus 6.1−20.4 s (lower by 15−39%) when ignited in a high-temperature medium without adding syngas to the combustion chamber. Based on the results obtained, a concept for the practical implementation of the CWS combustion technology in a syngas-modified oxidizer medium is proposed.