Photoluminescence, surface photovoltage spectroscopy and high-resolution characterization methods (Atomic Force Microscopy, Scanning Electron Microscopy, X-ray spectroscopy and DC conductivity) are applied to nanostructured Hydroxyapatite (HAp) bioceramics and allowed to study electron (hole) energy states spectra of the HAp and distinguish bulk and surface localized levels. The measured trap spectra show strong sensitivity to preliminary heat treatment of the ceramics. It is assumed that found deep electron (hole) charged states are responsible for high bioactivity of the HAp nanoceramics.