Ab initio simulation is one of the most effective theoretical tools to study the electrons evolved heat transfer process. Here, we report the use of finite-temperature density functional theory (DFT) to investigate the electron thermal excitation, electron–phonon coupled heat transfer, and the corresponding thermal response induced by energy deposition of femtosecond laser pulse in gold. The calculated results for cases with different scales of electron excitations demonstrate significant electron temperature dependence of electron heat capacity and electron–phonon coupling factor. Bond hardening of laser-irradiated gold and structural variation from solid to liquid are observed. The obtained results shed light upon the ultrafast microscopic processes of thermal energy transport from electron subsystem to lattice subsystem and serve for an improved interpretation of femtosecond laser–metal interaction.