A novel instrumentation has been made by coupling scanning tunneling microscopy (STM) with optical spectroscopic techniques that allow measurements of electronic band structures and, localized electronic states of isolated centers with an extremely high spatialresolution. The great analytical power of the STM-nanospectroscopy was demonstrated by presenting results of experiments on a nano-scale spatial variation of bandgap energy in a low-temperature grown (LT-) GaAs epi-film and photoabsorption spectra of isolated defects forming a localized energy level in the band gap.