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The influence of heating rate, gas flow, and biomass particle size on the pyrolysis and thermal dynamics of corncobs (CC) was investigated experimentally using the quantitative method of thermogravimetric analysis (TGA) coupled with mass spectrometry (MS), and the obtained results were compared in depth. For the examined heating rates of 5, 10, and 20 °C/min, the CC pyrolysis at higher heating rates resulted in a more complete decomposition. The initial pyrolysis temperature decreased when gas flow was increased from 30 to 90 mL/min, whereas the weight loss increased. Particle sizes (d ≤ 74 μm, 74 μm < d ≤ 154 μm, 154 μm < d ≤ 280 μm, and 280 μm < d ≤ 450 μm) had pronounced effects on the thermal decomposition and bio-syngas compounds (CO, CO2, CH4, and H2) distribution. The emission intensities of most the gaseous products increased at the elevated heating rate, while they decreased with increasing gas flow. In sum, the pyrolysis of CC particles of 154 μm < d ≤ 280 μm under 20 °C/min and in a gas flow of 30 to 60 mL/min was the most appropriate for bio-syngas production in industrial applications.