Mechanoluminescence (ML) has become the most promising material for broad applications in display and sensing devices, in which ZnS is the most commonly studied one due to its stable and highly repetitive ML performances. In this work, we have successfully prepared the biphase ZnS on a large scale through the facile in-air molten salt protection strategy. The obtained biphase has the best ML properties, which is mainly attributed to the synergistic effects of piezo-photonic, defect, and interface dislocations. DFT calculations have confirmed that the defects activate the local S and Zn sites and reduce the energy barrier for electron transfer. The much stronger X-ray induced luminescence than the commercial scintillator is also reached. The application of ZnS particles in both papers and inks delivers superior performance. Meanwhile, ZnS particles based screen printing ink is able to directly print on paper, plastic and other carriers to form clear marks. These proposed paper and ink hold great potentials in applications of information security and anti-counterfeiting based on the multi-mode luminescence properties. This work provides a new avenue to understand and realize the high-performance multi-mode luminescence, inspiring more future works to extend on other ML materials and boosting their practical applications.