We present a systematic investigation of the electronic properties of bulk and few layer ReS₂ van der Waals crystals using low temperature optical spectroscopy. Weak photoluminescence emission is observed from two non-degenerate band edge excitonic transitions separated by ∼20 meV. The comparable emission intensity of both excitonic transitions is incompatible with a fully thermalized (Boltzmann) distribution of excitons, indicating the hot nature of the emission. While DFT calculations predict bilayer ReS₂ to have a direct fundamental band gap, our optical data suggests that the fundamental gap is indirect in all cases.