Pressure-driven anomalous thermal transport behaviors in gallium arsenide

•Thermal properties of GaAs with multi-structure were measured up to ∼23 GPa.•Diverse heat carriers play a central role in κAl/GaAs in different regimes.•Lattice defects enable released GaAs to exhibit glass-like κ.•Both intrinsic and extrinsic factors enhance GAl/GaAs with compression.•The released GAl/GaAs is 2.6 times higher than that of the initial.