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We demonstrate Li+-doping engineering for improving the near-infrared (NIR) photoresponse in an Er3+-activated Y2O3 phosphor. We show that the rational incorporation of Li+ results in a large enhancement of the upconversion (UC) emission intensity up to 29 times upon excitation of NIR light. The improved UC properties could be associated with the enhanced dipole-dipole transition probability due to Li+-induced changes in the local site symmetry for Er3+ ions and improvement in the crystallinity of the samples. We further demonstrate the