We develop a photoluminescence-based technique to determine dopant profiles of localized boron-diffused regions in silicon wafers and solar cell precursors employing two excitation wavelengths. The technique utilizes a strong dependence of room-temperature photoluminescence spectra on dopant profiles of diffused layers, courtesy of bandgap narrowing effects in heavily-doped silicon, and different penetration depths of the two excitation wavelengths in silicon. It is fast, contactless, and nondestructive. The measurements are performed at room temperature with micron-scale spatial resolution. We apply the technique to reconstruct dopant profiles of a large-area (1 cm × 1 cm) boron-diffused sample and heavily-doped regions (30 μm in diameter) of passivated-emitter rear localized-diffused solar cell precursors. The reconstructed profiles are confirmed with the well-established electrochemical capacitance voltage technique. The developed technique could be useful for determining boron dopant profiles in small doped features employed in both photovoltaic and microelectronic applications.