In this paper, the synergistic effect of heavy fuel oil (HFO) and DPR Korea’s anthracite (KA) co-combustion was analyzed using thermogravimetric analysis (TGA). The TG-DTG-DSC results showed that the combustion stages of HFO could be roughly divided into four stages, whereas those of KA could be divided into three stages. The co-combustion process of HFO-KA mixtures differs from the combustion stages of HFO and KA. It could be divided into five stages; moisture dehydration (MD), low-temperature oxidation (LTO), fuel decomposition (FD), high-temperature oxidation (HTO) and fixed carbon burnout (CB). As the KA content ratio increased in HFO-KA mixtures, the maximum mass loss rate and maximum heat flow rate in the LTO and HTO stages decreased but increased in the CB stage. In order to analyze the synergistic effect of the mixing ratio, the TG-DTG-DSC experimental data of HFO-KA mixtures were compared with the predicted values calculated by the simple arithmetic average method. The synergistic effect according to the mixing ratio was found by comparative analysis of the experimental and predicted values. Compared with the 75 % HFO/75 % KA and 50 % HFO/50 % KA mixtures, experimental values of 25 % HFO/75 % KA mixture sample were superior to the predicted values, the synergistic effect was more obvious. Therefore, it concluded that when the co-combustion mixture with high ratio of KA, the synergistic effect was more obvious.