Developing efficiency and long‐lived room‐temperature phosphorescence (RTP) materials through straightforward methods is highly desired. In this work, a stepwise stabilization strategy was proposed by the coordination and in‐situ precipitation reactions among organic precursors, inorganic cation and anions, producing room‐temperature phosphorescence materials with high emission efficiency (phosphorescence quantum yield of 45%). Structural and photophysical characterizations revealed the coordination reaction reduced the energy gaps between singlet and triplet states and stabilized the excited states of the guest molecules. The in‐situ precipitation reaction produced a solid matrix, which provided isolated environments for protecting the excitons from quenching. The applications of RTP materials in information encryption were demonstrated. The presented results provided a new clue for producing RTP materials, and extended their applications in wide fields.