Investigating the impact of exciton-vibration coupling (EC) of molecular aggregates on regulating the excited-state dynamics and controlling room temperature phosphorescence (RTP) emissions is crucial and challenging. We designed and synthesized ArBFO molecules and cultured two crystals with similar molecular packing and completely different luminescent mechanisms from B-form fluorescence to G-form RTP. The mechanism study combining photophysical properties, time-resolved fluorescence analysis, X-ray diffraction analysis, and theoretical calculations shows that the tiny changes in molecular stacking amplify the EC value from B-form to G-form H-aggregates. The larger EC value accelerates the ISC process and suppresses the radiative singlet decay. Meanwhile, the stronger intermolecular interaction restricts the non-radiative transitions. These all facilities the green RTP emission in G-form. When treated with pressure-heating cycles, the transformation between B-form and G-form aggregates leads to a reversible blue fluorescence/green RTP switch with good reproducibility and photostability. Moreover, their potential in multi-level information encryption and anti-counterfeiting application have been well demonstrated. This research results deepen the understanding of the aggregation on luminescence mechanism and provide a new design guidance for developing smart materials with good performance.