Pollucite structures present remarkable chemical stability and good corrosion resistance against the leaching medium, which renders them promising for the permanent disposal of radioactive Cs-137. However, it is still challenging to prepare pollucite with dense structures and high immobilization performance at low temperature so far. Additionally, the fundamental understanding of the mechanism underlying the leaching behaviors of Cs+ from pollucite remains largely unexplored. In this paper, we realize the low-temperature production of pollucite by tailoring the nature of geopolymer precursors and employing B2O3 additives. It has been shown that the introduction of B2O3 not only significantly reduces the crystallization temperature of pollucite, but also improves the immobilization performance of Cs through encapsulation effect. Differential scanning calorimetry and X-ray diffraction confirm the formation of crystalline pollucite from amorphous geopolymer at similar to 700 degrees C in the presence of 7.5 wt% B2O3. By further increasing the treatment temperature to 1000 degrees C, pollucite grains can be well-encapsulated by glass phase, exhibiting leaching rates similar to 2 order lower than their unencapsulated counterparts. Moreover, distinct leaching mechanisms that govern the leaching behaviors of Cs+ from specimens being treated at different temperatures are unveiled. We anticipate that the proposed scheme facilitates the low-temperature production of high-quality pollucite structures with promising applications in the immobilization of hazardous wastes. (C) 2020 Elsevier B.V. All rights reserved.