Hole conducting, optically transparent Cu2O thin films on glass substrates have been synthesized by vacuum annealing (5×10-6 mbar at 700 K for 1 hour) of magnetron sputtered (at 300 K) CuO thin films. The Cu2O thin films are p-type and show enhanced properties: grain size (54.7 nm), optical transmission 72% (at 600 nm) and Hall mobility 51 cm2/Vs. The bulk and surface Valence band spectra of Cu2O and CuO thin films are studied by temperature dependent Hall effect and Ultra violet photo electron Spectroscopy (UPS). CuO thin films show a significant band bending downwards (due to higher hole concentration) than Cu2O thin films. © 2015 Author(s).