K-shell spectra of solid Al excited by petawatt picosecond laser pulses have been investigated at the Vulcan PW facility. Laser pulses of ultrahigh contrast with an energy of 160J on the targetallow studies of interactions between the laser field and solid state matter at 1020W/cm2. Intense X-ray emission of KK hollow atoms (atoms without n=1 electrons) from thin aluminum foils is observed from optical laser plasma for the first time. Specifically for 1.5μm thin foil targets the hollow atom yield dominates the resonance line emission. It is suggested that the hollow atoms are predominantly excited by the impact of X-ray photons generated by radiation friction to fast electron currents in solid-density plasma due to Thomson scattering and bremsstrahlung in the transverse plasma fields. Numerical simulations of Al hollow atom spectra using the ATOMIC code confirm that the impact of keV photons dominates the atom ionization. Our estimates demonstrate that solid-density plasma generated by relativistic optical laser pulses provide the source of a polychromatic keV range X-ray field of 1018W/cm2 intensity, and allows the study of excited matter in the radiation-dominated regime. High-resolution X-ray spectroscopy of hollow atom radiation is found to be a powerful tool to study the properties of high-energy density plasma created by intense X-ray radiation.