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The conversion of solid waste into energy through combustion is sustainable and economical. This study aims to comprehensively evaluate and quantify the co-combustion characteristics, synergistic catalysis, and gaseous pollutant emission patterns of sewage sludge (<i>SS</i>) and coal gasification fine slag residual carbon (<i>RC</i>) as well as their blends through thermogravimetry coupled with mass spectrometry (TG-MS). The results showed that the co-combustion of <i>SS</i> and <i>RC</i> can not only improve the ignition and burnout property but also maintain the combustion stability and comprehensive combustion performance at a better level. The kinetic analysis results showed that a first-order chemical reaction and three-dimensional diffusion are the reaction mechanisms during the co-combustion of <i>SS</i> and <i>RC</i>. The synergistic catalysis between <i>SS</i> and <i>RC</i> can well explain the changes in activation energy and reaction mechanism. Furthermore, the blending ratio of <i>SS</i> is recommended to be maintained at 40% because of the lowest activation energy (<i>E_a</i> = 81.6 kJ/mol) and the strongest synergistic effect (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mi>X</mi><mi>i</mi></msub></mrow></semantics></math></inline-formula> = 0.36). The emission of gaseous pollutants is corresponding to the primary combustion stages of <i>SS</i>, <i>RC</i>, and their blends. In co-combustion, the NH₃, HCN, NO_x, and SO₂ emissions gradually rise with the increase of <i>SS</i> proportion in the blends due to the high content of organic compounds in <i>SS</i>.