We demonstrate a potential optical thermometric material, Pr3+-doped triple-layered perovskite Na2La2Ti3O10 microcrystals, which promises a remarkable performance in temperature sensing over a wide temperature range (125-533 K), with a maximum relative sensitivity of 2.43% K-1 at 423 K. Both temperature and high-pressure dependent photoluminescence measurements were performed for this compound. It turns out that the Pr3+-Ti4+ intervalence charge transfer state is the primary cause for the very efficient thermometric characteristics in the 296-533 K range. In the 125-300 K range, 3P1 and 3P0 levels of Pr3+ can be exploited as thermally coupled energy levels for temperature sensing with high sensitivity at and below room temperature. A significant enhancement of the Pr3+ ions' luminescence observed in the 4.5-300 K range is ascribed to an efficient, thermally activated energy transfer process from the host to Pr3+ ions. Carrier recombination on Pr3+ related hole traps was proposed in the studied system. The thermoluminescence properties are investigated, and possible mechanisms for the interpretation of the experimental results are discussed as well. This work may provide a perspective approach to design a high-performance, self-calibrated optical thermometer operating over a wide temperature range.