Commercially available tenorite (CuO) nanoparticles (NPs) were investigated in particular with respect to their suitability for photovoltaic applications. NPs with a diameter of about 30 nm were step wise annealed up to 1000°C in nitrogen atmosphere. The influence of the annealing treatment on the structural and electronic properties was investigated by Raman, photoluminescence (PL) and photothermal deflection spectroscopy (PDS) as well as X-ray diffraction measurements. Size, shape, and phase of the untreated NPs are analyzed by TEM measurements. The PL and PDS results show a strong increase of the tenorite band edge emission at about 1.3 eV accompanied by a decreasing sub gap absorption with increasing annealing temperature up to 700°C. According to literature, a phase transition from tenorite to cuprite (Cu2O) was expected and observed after annealing at 800°C. Strong cuprite band edge emission at about 2 eV accompanied by very weak defect and possibly tenorite band edge emission was found for samples annealed at 800°C and 1000°C.