We report on the first observation of high-n hollow ions (ions having no electrons in the K or L shells) produced in Si targets via pumping by ultra-intense x-ray radiation produced in intense laser-plasma interactions reaching the radiation dominant kinetics regime (RDKR). The existence of these new types of hollow ions in high-energy density plasma has been found via observation of highly resolved x-ray emission spectra of silicon plasma. This has been confirmed by plasma kinetics calculations, underscoring the ability of powerful radiation sources to fully strip electrons from the innermost shells of light atoms. Hollow-ions spectral diagnostics provide a unique opportunity to characterize powerful x-ray radiation of laboratory and astrophysical plasmas. With the use of this technique we provide evidence for the existence of the RDKR via observation of asymmetry in the observed radiation of hollow ions from the front and rear sides of the target.