In this Letter, we present the observation of super-intense upconversion (UC) white emission of Yb2O3 under 980 nm excitation, its evolution on excitation power density, the UC mechanism, and its application on the luminescence converter of dye-sensitized solar cells (DSSCs). It is significant to observe that Yb2O3 demonstrates at least one order more intense UC luminescence than β-phase NaYF4:Yb3+, Er3+ and Yb2O3/DSSCs exhibit much better photovoltaic performance than β-phase NaYF4:Yb3+, Er3+/DSSCs under strong excitation. This indicates that Yb2O3 would become a novel candidate of the solar energy converter, especially in the application of concentrator solar cells.