Photoluminescence and absorption spectroscopy experiments were performed on as grown and thermally annealed GaAs1-xNx with nitrogen content in the range of 0.75–7.1%. At low temperature, the photoluminescence spectra exhibits two set of features: (i) a relatively broad peak at low energy and near to the vicinity of the predicted band gaps and (ii) a sharp excitonic feature at higher energy (about 100 meV for x>4%). Post growth thermal annealing processes systematically favor stronger excitonic emissions, and a notable intensity reduction of the deeper (defect related) luminescence. The low temperature binding energy of the higher energy excitonic peak is found to be consistent with the increase of the electronic effective masses. A careful examination of the data obtained in this work suggests that for higher nitrogen content (x>4%), the fundamental band gap of GaAsN is located at significantly higher energies than those commonly accepted for these alloys.