Room-temperature photovoltaic spectroscopy was applied to study undoped GaN, n-type GaN, and InGaN quantum well structures. Clear exciton absorption was observed in the photovoltaic spectra of the undoped GaN, and polarization measurements were made to identify the exciton absorption. For the n-type GaN sample, instead of the exciton absorption we observed only bulk absorption edge, which may be due to the free carrier screening effect. For the InGaN quantum well structures, the photovoltaic spectra showed relatively complicated line shape due to the overlap of the signals from different layers. By changing the reference phase of the lock-in amplifier, we were able to suppress some of the signals and thus identify the origin of the corresponding signal.