Surface photovoltage spectroscopy (SPS) has been employed to monitor optical transitions in quantum well and superlattice structures at room temperature. Excellent agreement is found between theoretical predictions of heavy hole and electron energy level positions and the observed transitions. The results show that using this technique, the complete band diagram of the quantum structure may be constructed. SPS emerges as a powerful tool capable of monitoring optical transitions above the lowest one in a simple to interpret, contactless, and nondestructive way.