Methyl 2-furoate (FAME2) pyrolysis was studied experimentally on a flow reactor in the temperature range of 879-1107 K and at the pressure of 760 Torr using synchrotron vacuum ultraviolet photoionization mass spectrometry. Several important intermediates were identified and measured, including the major pyrolysis products (methane, carbon monoxide, acetylene, formaldehyde, carbon dioxide, ketene, and vinyl acetylene) and even isomers of pyrolysis products (propyne, allene, 1,3-butadiene, 1-butyne, fulvene, and benzene). Unimolecular decomposition reactions in the pyrolysis of FAME2 were also studied theoretically at the CBS-QB3 level using the Gaussian procedure. Based on the calculated potential energy surface, a new kinetic model was developed and validated against our pyrolysis experiments. The rate of production and sensitivity analysis revealed that the decomposition reactions of FAME2 are mainly controlled by the unimolecular decomposition reactions, substitution reactions, H-abstraction reactions, and H-addition reactions in FAME2 pyrolysis. The dominant decomposition reaction is the direct release of CH3 from FAME2, which has about 42% contribution to the fuel consumption.