The gas-phase decomposition pathways of diethylzinc (DEZn), a common precursor for deposition of Zn-VI compounds, were investigated in detail. The homogeneous thermal decomposition of DEZn in N-2 carrier was followed in an impinging-jet, up-flow reactor by Raman scattering. Density Functional Theory calculations were performed to describe the bond dissociation behavior using the model chemistry B3LYP/6-311G(d) to estimate optimal geometries and Raman active vibrational frequencies of DEZn, as well as anticipated intermediates and products. Comparison of the measured DEZn decomposition profile to that predicted by a 2-D hydrodynamic simulation revealed that simple bond dissociation between zinc and carbon atoms is the dominant homogeneous thermal decomposition pathway. The calculations suggest several reactions involving intermediates and Raman scattering experiments confirming the formation of the dimer (ZnC2H5)(2), In a different set of experiments, photolysis of DEZn gave evidence for decomposition by beta-hydride elimination. The results suggest that beta-hydride elimination is a minor pathway for the gas-phase homogeneous pyrolysis of diethylzinc. A reasonable transition state during beta-hydride elimination was identified, and the calculated energies and thermodynamic properties support the likelihood of these reaction steps.