As twinning-induced plasticity (TWIP) steel is one potential material for shaped charge liner due to the combination of high strength and high plasticity, deformation mechanism at high strain rate and high temperature is required to study. Compression experiments of Fe-30Mn-3Si-4Al TWIP steel were conducted using a Gleeble-1500 thermal simulation machine and a split-Hopkinson pressure bar (SHPB) between 298 and 1073 K at strain rates of 10-3 and 700 s-1, respectively. Microstructures were observed using optical microscopy (OM) and transmission electron microscopy (TEM). Results show that flow stress and densities of deformation twins and dislocations decrease with increasing deformation temperature at strain rates of 10-3 and 700 s-1. The stack fault energy (SFE) values (Γ) of Fe-30Mn-3Si-4Al TWIP steel at different temperatures were calculated using thermodynamic data. Based on corresponding microstructures, it can be inferred that at 700 s-1, twinning is the main deformation mechanism at 298-573 K for 30 mJ/m2≤Γ≤63 mJ/m, while dislocation gliding is the main deformation mechanism above 1073 K for Γ≥ 145 mJ/m2. In addition, with increasing strain rate from 10-3 to 700 s-1, the SFE range of twinning is enlarged and the SEF value of twinning becomes higher.