Acting as a highly nonlinear response to the strong laser field, high
harmonic generation (HHG) naturally contains the fingerprints of atomic and
electronic properties of materials. Electronic properties of a solid such as
band structure and topology can thus be probed, while the phonon dynamics
during HHG are often neglected. Here we show that by exploiting the effects of
phonon deformation on HHG, the intrinsic phonon information can be deciphered
and direct probing of band- and mode-resolved electron-phonon couplings (EPC)
of photoexcited materials is possible. Considering HHG spectroscopy can be
vacuum free and unrestricted to electron occupation, this work suggests HHG is
promising for all-optical characterization of EPC in solids, especially for
gapped quantum states or materials under high pressure