Studies of 3-methylfuran (MF3) pyrolysis were carried out from 848 to 1373 K in a pyrolysis tube at 30 and 760 Torr using synchrotron vacuum ultraviolet photoionization mass spectrometry. Key products and intermediates were detected and measured, including methyl, propargyl, acetylene, ethylene, propyne/allene, vinylacetylene, propene, 1,3-butadiene, 2-butyne, ketene, etc. A pyrolysis model of MF3 was constructed and validated against the experimental data. The reaction pathways of MF3 decomposition, aromatics formation, and comparison between MF3 and 2-methylfuran pyrolysis were analyzed. The pyrolysis of MF3 was mainly controlled by the H-transfer reaction at 30 Torr. The H-transfer reaction and H-abstraction reaction dominated the consumption of MF3 at 760 Torr. MF3 had similar consumption pathways and slightly lower aromatics formation tendency than those of 2-methylfuran.