Cu2S, featuring low cost, nontoxicity, and earth abundance, has been recently recognized as a high efficiency thermoelectric (TE) material. However, before reaching the maximum of the figure of merit (ZT), Cu2S undergoes three phase transformations starting at 370 K, which give rise to severe problems, such as possible decomposition and low reliability. Herein, we discover CsCu5S3 with phase transformation at 823 K, which is significantly higher than the 370 K value of Cu2S. Single crystal diffraction data reveal that its two phases are constructed by the same Cu4S4 columnar building unit via propagating either at the opposite sides into a layered o-CsCu5S3, or at the four apexes into a 3D t-CsCu5S3, respectively. Interestingly, the o-to-t transformation is quick, but the reverse one is relatively slow. Theoretical studies reveal that the Cu4S4 column exhibits not only the most condensed atomic aggregation (D-column) but also the lightest effective mass (m*), along which higher a is realized. More interestingly, both phases exhibit remarkable ZT enhancements, 0.46 at 800 K for o-CSCU5S3, and 0.56 at 875 K for t-CsCu5S3, which are 170% and 175% that of Cu2S at the same temperature.