Tremendous success has been achieved in photovoltaic (PV) applications, but PV-generated electricity still cannot compete with traditional power in terms of price. Chemically stable and nontoxic all-oxide solar cells made from earth-abundant resources fulfill the requirements for low-cost manufacturing under ambient conditions and thus are promising as the next-generation approach to solar cells. However, the main obstacles to developing all-oxide solar cells are the spectral absorbers. Besides photovoltaics, novel chemically stable, nontoxic, and earth-abundant narrow-bandgap semiconductors are desired for photochemical applications in photodetectors, photoelectrodes, or photocatalysts. Herein, were report novel lead-free perovskite narrow-bandgap rare-earth semiconductors, YMnO 3 , HoMnO 3 , ErMnO 3 , and YbMnO 3 , which were identified by screening a family of perovskite rare-earth manganates, RMnO 3 (R = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Yb). The sharp edge observed in their absorption spectra indicates the existence of band gaps, further confirmed with laser Raman fluorescence spectra. Good periodic on−off photoelectronic response was observed in 8 of the 12 members (i.e., R = La, Pr, Nd, Sm, Gd, Tb, Dy, and Yb). Among them, YbMnO 3 is approved as an n-type semiconductor with a direct band gap near 1.35 eV, whose theoretical Shockley−Queisser efficiency is approximately 33.7% for single-p−n-junction solar cells. This work sheds light on exploring stable oxide semiconductors with a narrow band gap for future applications.