CsPbI₃ quantum dots (QDs) hold tremendous promise for quantum emitters, but they undergo a considerable energy loss when excited above their optical bandgap, which impedes the utilization of high-energy photons. Different surface modification strategies have been proposed to improve the phase stability of CsPbI₃ QDs, however, little progress has been made to realize high photoluminescence quantum yield (PLQY) with high-energy photon excitation. Here, a non-resonant barrier excitation (NRBE) mechanism in conjugated aromatic tetraphenylporphyrin (H₂TPP)-modified CsPbI₃ QDs is presented, which enables a high PLQY in the high-energy excitation regime as well as enhanced phase stability. Particularly, the proposed H₂TPP ligand possesses adequate energy depth needed to realize NRBE in CsPbI₃ QDs, which allows efficient charge injection from organic ligands to the inorganic core. As a result, the H₂TPP-modified CsPbI₃ QDs exhibit enhanced light absorption, large Stokes shift, and near-unity red emission when excited above the optical bandgap. The findings provide new insights into the ligand design strategies for improving optoelectronic properties.